CATALYTIC COMPOSITION COMPRISING CATALYTIC ACTIVATED
CARBON AND CARBON NANOTUBES, MANUFACTURING PROCESS.
ELECTRODE AND SUPER CAPACITATOR COMPRISING THE CATALYTIC
COMPOUND
The invention relates to a catalytic composition comprising a polymer binder and
a catalytic composite based on catalytic activated charcoal and carbon nanotubes, and to
the use of the composition as constituent material for electrodes intended especially for
electrochemical double-layer energy storage cells (supercapacitors). The invention also
relates to the electrodes obtained and to the supercapacitors containing these composite
materials.
Storage cells called "supercapacitors" or EDLCs (Electric Double Layer
Capacitors) consist of current collectors to which an activated substance comprising
carbon materials is applied. This system is then immersed in a solvent containing a salt
and allows electrical energy to be stored for subsequent use.
Energy storage cells must display a good compromise between energy density
and power density, and also improved behaviour in respect of the internal resistance
and/or a maintained capacitance for high current densities. Furthermore, these cells must
exhibit good ageing properties.
The carbon materials supplied to collectors consist to a large part of charcoal. In
recent years, electrodes based on a physical mixture of carbon nanotubes (CNTs) and
activated charcoal (AC) have been developed. Thus, Liu et al. (Chinese Journal of
Power Sources, Vol. 26, No. 1, 36, February 2002) have described such electrodes.
Tokin et al (JP 2000-124079 A) have described polarizable electrodes, consisting
of a composition comprising charcoal, open-ended carbon nanotubes and binder,
obtained by simple physical mixing of the constituents.
CN 1 388 540 discloses a composite consisting of carbon nanotubes and
activated charcoal that are doped with transition metal oxides and with conductive
polymers in order to obtain charge-accumulation EDLCs.
Recently, the Applicant in WO 2005/088657 A2 has described a method for
manufacturing electrodes based on a mixture of activated charcoal and carbon nanotubes
that also exhibit good ageing properties.
However, the Applicant has found that physical mixtures of carbon nanotubes,
activated charcoal and binder result in the density of the electrode being lowered, to the
detriment of the capacitance per unit volume or per unit mass.
With the present invention, the Applicant therefore proposes a catalytic
composition comprising a polymer binder and carbon nanotubes obtained by chemical

vapour deposition of a hydrocarbon, in particular ethylene, at a temperature ranging
from 400 to 1100°C on activated charcoal preimpregnated with a metal, the metal being
selected from the transition metals Fe, Co, Ni and Mo, and preferably iron.
The catalytic composite mixed with a binder makes it possible to obtain a
composition for coating electrodes, the properties of which are improved, in particular
those relating to the conductivity, the capacitance per unit volume as a function of the
current density, or else the ageing resistance.
According to one embodiment, the weight ratio of metal-impregnated activated
charcoal to carbon nanotubes present in the catalytic composite ranges from 98/2 to
80/20.
According to one embodiment, the amount of impregnated metal on the activated
charcoal is between 1.5 and 15 %, preferably between 1.5 and 10%.
According to a preferred embodiment, the activated charcoal has the following
characteristics:
a) porosity:
• microporous volume (diameter < 2 nm) determined by the DFT method
ranges from 0.5 cm3/g to 0.65 cm3/g and representing at least 75 % and
preferably at least 78 % of the total porosity of said charcoal,
• nitrogen BET specific surface area between 1000 and 1600 m2/g,
preferably between 1200 and 1600 m2/g ;
b) purity :
• pH between 5 and 8, preferably about 7, and total ash content, determined
by the ASTM D2866-83 method, less than 1.5 % by weight,
• the percentage contents by weight of the following impurities, determined
by mineralization (HNO3/H2O2 treatment) followed by analysis by ICP
emission spectrometry or, in the case of chlorides, by extraction with
water followed by analysis by ion chromatography, are such that:
• [chlorides] < 80 ppm
• [chromium] < 20 ppm
• [copper] < 50 ppm
• [iron] < 300 ppm
• [manganese] < 20 ppm
• [nickel] < 10 ppm
• [zinc] < 20 ppm
c) particle size distribution, determined by laser scattering, such that:
3 um < d50 < 15 µrn
10 µm < d90 < 60 µm; and

d) pH, determined by the CEFIC method, between 3.5 and 9, preferably between
4.5 and 8.
Preferably, the binder is selected from elastomers and thermoplastic polymers or
blends thereof, preferably polyethers, polyalcohols, ethylene/vinyl acetate (EVA)
copolymers, fluoropolymers and styrene/butadiene copolymers.
According to one embodiment, the binder is selected from polyoxyethylene
(POE), polyoxypropylene (POP), polyvinyl alcohol (PVA), polytetrafluoroethylene
(PTFE) and styrene/butadiene copolymers.
According to another embodiment, the binder is an aqueous suspension of PTFE
or of a styrene/butadiene copolymer.
The proportion of binder ranges from 1% to 30% by weight relative to the
amount of catalytic composite.
According to another subject, the invention relates to a method of preparing an
electrode based on a catalytic composite containing activated charcoal and carbon
nanotubes on a collector, comprising the following steps :
a. preparing a catalytic composite by a method comprising the following
steps;
i. the activated charcoal is mixed with a solution of a metal
salt, preferably an aqueous solution comprising a nitrate or a
sulphate;
ii. the mixture is dried, the metal salt is then reduced and the
activated charcoal impregnated with metal in metallic form is
obtained; and
iii. carbon nanotubes are synthesized on the activated charcoal
obtained in step ii) by chemical vapour deposition (CVD) of a
hydrocarbon at a temperature ranging from 400 to 1100°C;
b. mixing of the catalytic composite with a solvent, preferably by
ultrasonification;
c. addition of a polymer binder and mixing until homogenization;
d. drying of the paste;
e. optionally, kneading of the paste; and
f. coating and then drying of the collector.
According to a preferred mode, step b) is carried out at a temperature above
20°C, preferably in ethanol.
According to a preferred mode, step e) is carried out until fibrillation of the
binder.
According to another subject, the invention relates to a method of preparing a
paste based on a catalytic composite, comprising steps a) to e) described above.

According to yet another subject, the invention relates to an electrode with
improved ageing, obtained by the method comprising steps a) to f) as described above.
According to yet another subject, the invention relates to an electrochemical
supercapacitor comprising at least one electrode with improved ageing, as described
above.
According to yet another subject, the invention relates to the use of a composition
as described above in the form of a paste for coating electrode collectors.
The invention will now be described in greater detail in the description that
follows.
The invention provides a composition comprising a binder and a catalytic
compositecomprising catalytic activated charcoal doped with carbon nanotubes. This
catalytic composite is obtained by direct synthesis of carbon nanotubes on a catalytic
activated charcoal. This composition, applied to a collector, makes it possible to obtain
electrodes with improved ageing.
The invention also provides a method of preparing the composition and the
electrodes comprising this composite.
The electrodes based on such catalytic materials have improved properties from
the standpoint of conductivity, capacitance per unit volume as a function of the current
density and/or ageing resistance. Likewise, the energy storage cells comprising these
electrodes exhibit a very good compromise between energy density and power density.
The invention is also based on a method of preparing electrodes comprising
collectors to which a carbon paste consisting of at least one catalytic composite is
applied. The method of preparing the carbon paste comprises the following steps :
a) a catalytic composite comprising catalytic activated charcoal and carbon
nanotubes is provided;
b) the catalytic composite in suspension in the solvent is mixed, in particular
ultrasonically mixed for a time of between 5 and 60 minutes for example (at a
temperature above 20°C, for example between 20 and 80°C);
c) the binder is added until a homogeneous mixture is obtained ;
d) a drying operation is carried out in order to evaporate the solvent
e) optionally, the paste is kneaded, in order to fibrillate the binder, especially
when PTFE is used ; and
f) the collectors are coated and then dried
Without prejudicing the correction operation of the method, steps b) and c) may
be carried out at the same time. Step d) may also be carried out after step f), and in this
case the solvent evaporation allows final drying of the electrodes.
This catalytic composite is prepared by direct growth of carbon nanotubes on an
activated charcoal preimpregnated with a metal according to the following method:

i. activated charcoal is mixed with a solution of a metal salt;
ii. the mixture is dried, the metal salt is then reduced and activated charcoal
impregnated with metal in metallic form, that is to say a metal in the zero
valency state is obtained; and
iii. the carbon nanotubes are synthesized on the metal-impregnated activated
charcoal by chemical vapour deposition (CVD) of a hydrocarbon at a
temperature ranging from 400 to 1100°C.
Carbon nanotubes (CNTs) are also known and generally consist of one or more
wound graphite sheets, i.e. SWNTs (single-walled nanotubes) or MWNTs (multi-walled
nanotubes). These CNTs are commercially available or else may be prepared by known
methods.
The activated charcoal used is of any type of charcoal conventionally used.
Charcoals that may be mentioned include those obtained from lignocellulosic materials,
(pine, coconut, etc.). Examples of activated charcoals that may be mentioned include
those described in the application WO-A-02/43088 in the name of the Applicant. Any
other type of activated charcoal is effective. The activated charcoal may be obtained by
chemical activation or preferably by thermal or physical activation. The activated
charcoal is preferably ground to a size, expressed as d50, of less than about 30 microns
and preferably to a d50 of about 10 microns. The ash content of the charcoals is
preferably less than 10%, advantageously less than 5%. These activated charcoals are
commercially available or may be prepared by known methods.
Preferably, the charcoals selected have a micropore volume of greater than
0.35 cm3/g and a ratio of the micropore volume to the total pore volume of greater than
60 %, these volumes being measured by N2 adsorption using the DFT method with slit
pores. Preferably, the activated charcoals selected have the following characteristics:
a) porosity :
• microporous volume (diameter < 2 nm) determined by the DFT method
ranging from 0.5 cm3/g to 0.65 cm3/g and representing at least 75 % and
preferably at least 78 % of the total porosity of said carbon,
• nitrogen BET specific surface area between 1000 and 1600 m2/g,
preferably between 1200 and 1600 m2/g ;
b) purity :
• pH between 5 and 8, preferably about 7, and total ash content, determined
by the ASTM D2866-83 method, less than 1.5 % by weight,
• the percentage contents by weight of the following impurities, determined
by mineralization (HNO3/H2O2 treatment) followed by analysis by ICP
emission spectrometry or, in the case of chlorides, by extraction with
water followed by analysis by ion chromatography, are such that:

• [chlorides] < 80 ppm
• [chromium] < 20 ppm
• [copper] < 50 ppm
• [iron] < 300 ppm
• [manganese] < 20 ppm
• [nickel] < 10 ppm
• [zinc] < 20 ppm
c) particle size distribution, determined by laser scattering, such that :
3 um < d50 < 15 µm
10 µm < d50 < 60 µm; and
d) pH, determined by the CEFIC method, between 3.5 and 9, preferably between
4.5 and 8.
The activated charcoal is doped using a solution of a metal salt. The activated
charcoal obtained is called a catalytic charcoal.
The metal used to dope the activated charcoal is a transition metal chosen from
Fe, Co, Ni and Mo, and is preferably iron.
The metal used may be in any oxidized form, whether or not hydrated, preferably
in the form of an oxide, hydroxide, nitrate or sulphate.
In general, the metal salt is dissolved in a solvent, which may be water, and it is
mixed with the activated charcoal so as to obtain the metal-salt-impregnated activated
charcoal. Advantageously, aqueous solutions of iron nitrates or sulphates, preferably
hydrated, are used.
The amount of impregnated metal on the activated charcoal is between 1.5 and
15%, preferably between 1.5 and 10%, by weight relative to the amount of activated
charcoal introduced.
Next, the operation of drying the mixture is carried out. This drying operation is
generally carried out at a sufficient temperature and for a sufficient time to obtain a
handleable state of the mixture.
The metal salt, preferably the iron salt, impregnating the activated charcoal with
salt is then raised in temperature in nitrogen for example up to 300°C when iron is used
as metal. This temperature rise has the effect of decomposing the iron salt, before its
reduction to metal in the zero valency state.
The reduction step is then generally carried out in a hydrogen atmosphere at a
temperature that may be up to 800°C, preferably up to 650°C, for a time needed to result
in the reduction of the metal salt, preferably for 10 to 30 minutes. These temperature and
time parameters are readily defined by a person skilled in the art and easily adaptable to
a different metal salt.

The carbon nanotubes are then synthesized on the metal-impregnated activated
charcoal thus obtained, by chemical vapour deposition (CVD) of a hydrocarbon at a
temperature ranging from 400 to 1100°C, preferably 300°C. The hydrocarbon used is
preferably ethylene.
The amount of CNT synthesized on the catalytic activated charcoal ranges from 1
to 50%, preferably 2 to 20%. This amount depends on the time devoted to the CVD.
Thus, the catalytic composite has a catalytic activated charcoal or metal-impregnated
activated charcoal/CNT weight ratio that ranges from 99/1 to 50/50, preferably from
98/2 to 80/20.
Thus, with the method according to the invention, what is obtained is a catalytic
composite the pores of the active charcoal of which have not been saturated with CNTs,
which composite therefore contains a small amount of carbon nanotubes.
This catalytic composite makes it possible, as explained below, to prepare a
carbon paste that is applied to electrode collectors, the electrodes of which consequently
have improved properties. The method of preparing the carbon paste comprises the
above mentioned steps b) to f).
In step b), the catalytic composite is mixed with a solvent. The solvent used may
be any aqueous or organic solvent compatible with the raw materials to be dispersed,
such as acetonitrile or ethanol. This solvent, which is used to adjust the plasticity of the
paste, is preferably an evaporable solvent.
The amount of binder introduced in step c) represents from 1 to 30%, preferably
2 to 10%, by weight relative to the amount of catalytic composite present. Thus, the
carbon paste obtained after homogenizing and drying the polymer binder/catalytic
composite mixture contains a catalytic composite/polymer binder weight ratio that
ranges from 99/1 to 70/30, preferably from 98/2 to 90/10.
The polymers used as polymer binder may for example be elastomers or
thermoplastic polymers or blends thereof that are soluble in said solvent. Among these
polymers, polyethers, such as polyoxyethylene (POE), polyoxypropylene (POP) and/or
polyalcohols, such as polyvinyl alcohol (PVA), ethylene/vinyl acetate (EVA)
copolymers, fluoropolymers, such as polytetrafluoroethylene (PTFE), and
styrene/butadiene (SB) copolymers may in particular be mentioned. It is advantageous to
use binders in aqueous suspension.
The invention also relates to the carbon paste, obtained by the method according
to the invention, intended for coating electrode collectors.
The catalytic composite comprising carbon nanotubes obtained by chemical
vapour deposition of a hydrocarbon at a temperature ranging from 400 to 1100°C on an
activated charcoal preimpregnated with a metal may be considered as an intermediate
product for obtaining the carbon paste according to the invention.

The invention also relates to the electrodes manufactured using the above
method.
In the manufacture of such electrodes, it is possible to use other constituents and
third bodies, such as carbon blacks.
These electrodes are useful for the manufacture of electrochemical double-layer
energy storage cells (EDLC supercapacitors).
An EDLC-type supercapacitor is composed of: a pair of electrodes (1), one (and
preferably both) of which is an electrode with a carbon paste according to the invention;
a porous ion-conducting separator (2) comprising an electrolyte; and a non-ionically
conducting collector (3) for making electrical contact with the electrodes.
Manufacture of the electrodes (1), starts with the paste or slurry obtained as
described above, which will be applied to a support and the solvent then evaporated in
order to form a film. Next, the paste obtained is applied to a support, especially by
coating. It is advantageous for the coating to be carried out on a peelable support, for
example using a template, generally of flat shape.
Next, the solvent is evaporated, for example under a hood. What is obtained is a
film whose thickness depends especially on the charcoal paste concentration and on the
deposition parameters, the thickness generally being between a few microns and 1
millimetre. For example, the thickness is between 100 and 500 microns.
Suitable electrolytes to be used for producing EDLC supercapacitors consist of
any highly ionically conducting medium, such as an aqueous solution of an acid, a salt
or a base. If desired, non aqueous electrolytes may also be used, such as tetraethyl
ammonium tetrafluoroborate (Et4NBF4) in acetonitrile, or γ-butyrolactone or propylene
carbonate.
One of the electrodes may be composed of another material known in the art.
Between the electrodes is a separator (2) generally made of a. highly porous
material, the functions of which are to ensure electronic isolation between the electrodes
(1), whilst still allowing ions to pass through the electrolyte. In general, any
conventional separator may be used in an EDLC supercapacitor of high power density
and energy density. The separator (2) may be an ion-permeable membrane that allows
ions to pass through it but prevents electrons from passing through it.
The ion-impermeable current collector (3) may be any electrically conducting
material that is not an ion conductor. Satisfactory materials to be used to produce these
collectors comprise: charcoal, metals in general, such as aluminium, conducting
polymers, non-conducting polymers filled with a conducting material so as to make the
polymer electrically conducting, and similar materials. The collector (3) is electrically
connected to an electrode (1).

The manufacturing method and the energy storage cell according to the invention
will be described in greater detail in the following examples. These examples are
provided by way of illustration but imply no limitation of the invention.
Examples
Preparation of the storage cells/measurement:
In the examples, the electrodes were manufactured as follows:
ultrasonic mixing of 95% of a charcoal/nanotube catalytic composite, in
suspension in 70% ethanol, for 15 minutes followed by addition of 5% PTFE as a
60 wt% aqueous suspension;
evaporation and kneading of the paste in the presence of ethanol until
complete fibrillation of the PTFE;
drying of the paste at 100°C, and
coating of the 100 to 500 microns thick aluminium collectors with the
paste in order to form the electrode. The collectors are made of 99.9 % aluminium and
the total thickness, after lamination, was 350 to 450 microns.
The catalytic composite was obtained by directly synthesizing nanotubes on the surface
of the activated charcoal into which a metal had been deposited beforehand.
The cells were assembled in a glove box in an atmosphere having a controlled
content of water and oxygen, the contents being less than 1 ppm. Two square electrodes
4 cm2 in area were taken and a separator made of a microporous polymer inserted
between them. The whole element was held in place with two PTFE shims and two
stainless steel clips and then placed in an electrochemical cell containing the electrolyte
(an acetonitrile/tetraethyl ammonium tetrafluoroborate mixture).
In the examples, the electrochemical measurement protocol was the following:
galvanostatic cycling: a constant current of +20 mA or -20 mA was
imposed at the terminals of the capacitor and a charge-discharge curve generated: the
variation in the voltage was monitored as a function of time between 0 and 2.3 V. The
capacitance was deduced from the discharge slope of the capacitor, the capacitance
being expressed per electrode and per gram of active material, by multiplying this value
by two and by dividing by the mass of active material. The resistance was measured by
impedance spectroscopy. This test consisted in subjecting the capacitor to a low-
amplitude sinusoidal voltage of variable frequency around an operating point (Vs = 0; Is
= 0). The response current was out of phase with the excitation voltage. The complex
impedance was therefore the ratio of the voltage to the current, similar to a resistance.
The resistance was expressed as the real part of the impedance, for a frequency of 1 kHz,
multiplied by the area of the electrode; and
ageing tests carried out in the following manner: ±100 raA/cm2
galvanostatic cycling was carried out between 0 and 2.3 volts. The capacitance was

deduced directly from the discharge line of the supercapacitor and the resistance was
measured at each end of charging by a series of 1 kHz current pulses. The measurements
taken at each cycle are used to monitor the variation in the capacitance and the resistance
of the supercapacitor as a function of the number of charge/discharge cycles. The
cycling was carried out for as many cycles as needed to estimate the ageing.
Example 1 (control):
The activated charcoal used was that called "Acticarbone" sold by the company
CECA.
The charcoal tested had a d50 particle size, estimated by laser scattering, of around 8
microns and was subjected to an additional treatment in a liquid phase for lowing the ash
content. Its pH was about 6.5.
The BET surface area and the pore volumes, determined by the DFT (slit pore)
method were as indicated below:
specific surface area = 1078 m2/g;
micropore (< 2 nm) volume = 0.5 cm3/g;
mesopore (2-50 nm) volume = 0.15 cm3/g; and
macropore (> 50 nm) volume = 0.1 cm3/g.
9.5 g of this charcoal were mixed in 100 ml of water with 0.5 g of MWNT
carbon nanotubes sold by Arkema, the mixture being ultrasonically treated for 10
minutes, and the resulting paste was dried at 110°C.
The characteristics of these nanotubes were:
specific surface area = 220 m2/g;
Fe=1.7%;
Al = 2.2 %; and
d50 (Malvern) = 40 microns.
The properties of this physical charcoal/carbon nanotube mixture are given in
Table I.
Example 2:
Catalytic activated charcoal 1
The catalytic activated charcoal on which carbon nanotubes were to be
synthesized was prepared by impregnating 100 g of Acticarbone charcoal by means of
80 ml of an iron nitrate nonahydrate solution so as to deposit 2.5 wt% iron into the
activated charcoal. The deposition was carried out over 10 minutes at room temperature.
This specimen was called catalytic activated charcoal 1.
Catalytic activated charcoal 2
The operation was repeated by depositing 5 wt% iron using an equivalent
method. This specimen was called catalytic activated charcoal 2.

After deposition, the impregnated charcoals were dried at 80°C and then
introduced into a vertical reactor 25 cm in diameter and 1 m in height, in which they
were heated in nitrogen up to 300°C.
This temperature was maintained for the purpose of decomposing the iron salt,
but another temperature suitable for a different salt would not be outside the scope of the
invention.
The nitrogen flow rates were selected so as to ensure slight fluidization, for
example 2 to 4 S1/h. Next, a quarter of the nitrogen gas flows was replaced with
hydrogen in order to reduce the iron salt, the temperature was raised to 650°C , where it
remained for 20 minutes. At that moment, the nitrogen was replaced with ethylene in
order to initiate the growth of carbon nanotubes on the catalytic activated charcoal.
The following trials were carried out:
Trial 1: composite 1 (C1)
Catalytic activated charcoal: 1 and 15 minutes of carbon nanotube synthesis.
The weight increase of the recovered material, corresponding to the amount of
CNT grown on the catalytic activated charcoal, was about 6 %.
Trial 2: composite 2 (C2)
Catalytic activated charcoal: 1 and 45 minutes of carbon nanotube synthesis.
The weight increase of the recovered material, corresponding to the amount of
CNT grown on the catalytic activated charcoal, was about 13 %.
Trial 3: composite 3 (C3)
Catalytic activated charcoal: 1 and 15 minutes of carbon nanotube synthesis.
The weight increase of the recovered material, corresponding to the amount of
CNT grown on the catalytic activated charcoal, was about 5 %.
Example 3:
The electrochemical assembly described above was prepared from composite 1
and the performance measured.
Example 4:
The electrochemical assembly described above was prepared from composite 2
and the performance measured.
Example 5:
The electrochemical assembly described above was prepared from composite 3
and the performance measured.
The results are given in Table I below:


This shows that the method proposed by the invention makes it possible to
increase the density of the electrodes over that of the prior art. This increase in their
density correspondingly increases their capacitance per unit weight, while maintaining
their resistance.
In addition, the ageing tests show that the method proposed by the invention
makes it possible to maintain the density of the electrode and consequently to retain their
capacitance per unit weight, while still maintaining the other performance characteristics
such as the resistance. This means that the energy density of the system according to the
invention is maintained at least as well as, if not better than, that of the prior art.

CLAIMS.
1. Catalytic composition comprising a polymer binder and carbon nanotubes
obtained by chemical vapour deposition of a hydrocarbon at a temperature ranging
from 400 to 1100°C on activated charcoal preimpregnated with a metal.
2. Composition according to Claim 1, in which the hydrocarbon is ethylene.

3. Composition according to either of Claims 1 and 2, in which the metal is selected
from the transition metals Fe, Co, Ni and Mo, preferably iron.
4. Composition according to one of Claims 1 to 3, in which the weight ratio of
metal-impregnated activated charcoal to carbon nanotubes present in the catalytic
composite ranges from 98/2 to 80/20.

5. Composition according to one of Claims 1 to 4, in which the amount of
impregnated metal on the activated charcoal is between 1.5 and 15 %, preferably
between 1.5 and 10%.
6. Composition according to one of Claims 1 to 5, in which the activated charcoal
has the following characteristics:
a) porosity :
• microporous volume (diameter < 2 nm) determined by the DFT method
ranges from 0.5 cm3/g to 0.65 cm3/g and representing at least 75 % and
preferably at least 78 % of the total porosity of said charcoal,
• nitrogen BET specific surface area between 1000 and 1600 m2/g,
preferably between 1200 and 1600 m2/g ;
b) purity:
• pH between 5 and 8, preferably about 7, and total ash content, determined
by the ASTM D2866-83 method, less than 1.5 % by weight,
• the percentage contents by weight of the following impurities, determined
by mineralization (HNO3/H2O2 treatment) followed by analysis by ICP
emission spectrometry or, in the case of chlorides, by extraction with
water followed by analysis by ion chromatography, are such that:
• [chlorides] < 80 ppm
• [chromium] < 20 ppm
• [copper] < 50 ppm
• [iron] < 300 ppm

• [manganese] < 20 ppm
• [nickel] < 10 ppm
• [zinc] < 20 ppm
c) particle size distribution, determined by laser scattering, such that:
3 um < d50 < 15 um
10 um < d90 < 60 µm; and
d) pH, determined by the CEFIC method, between 3.5 and 9, preferably between
4.5 and 8.
7. Composition according to one of Claims 1 to 6 , in which the binder is selected
from elastomers and thermoplastic polymers or blends thereof, preferably polyethers,
polyalcohols, ethylene/vinyl acetate (EVA) copolymers, fluoropolymers and
styrene/butadiene copolymers.
8. Composition according to one of Claims 1 to 7, in which the binder is selected
from polyoxyethylene (POE), polyoxypropylene (POP), polyvinyl alcohol (PVA),
polytetrafluoroethylene (PTFE) and styrene/butadiene copolymers.

9. Composition according to one of Claims 1 to 98 in which the binder is an
aqueous suspension of PTFE or of a styrene/butadiene copolymer.
10. Composition according to one of Claims 1 to 9, in which the proportion of binder
ranges from 1% to 30% by weight relative to the amount of catalytic composite.
11. Method of preparing an electrode based on a catalytic composite containing
activated charcoal and carbon nanotubes on a collector, comprising the following
steps :
a preparing a catalytic composite by a method comprising the following
steps;
i. the activated charcoal is mixed with a solution of a metal salt;
ii. the mixture is dried, the metal salt is then reduced and the activated
charcoal impregnated with metal in metallic form is obtained; and
iii. carbon nanotubes are synthesized on the activated charcoal obtained in
step ii) by chemical vapour deposition (CVD) of a hydrocarbon at a
temperature ranging from 400 to 1100°C
b. mixing of the catalytic composite with a solvent;
c. addition of a polymer binder and mixing until homogenization;

d. drying of the paste;
e. optionally, kneading of the paste; and
f. coating and then drying of the collector.
12. Method according to Claim 11, in which the metal salt solution is an aqueous
solution comprising a nitrate or a sulphate.
13. Method according to either Claim 11 or 12, in which step b) is carried out by
ultrasonification.
14. Method according to one of Claims 11 to 13, in which step b) is carried out at a
temperature above 20°C.
15. Method according to one of Claims 11 to 14, in which step e) is carried out until
fibrillation of the binder.
16. Method according to one of Claims 11 to 15, in which the solvent of step b) is
ethanol.
17. Method according to one of claims 11 to 16 of preparing a paste based on a
catalytic composite, comprising the steps
a preparing a catalytic composite by a method recited in steps i to iii of any
one of claims 11 to 16
b. mixing of the catalytic composite with a solvent;
c. addition of a polymer binder and mixing until homogenization;
d. drying of the paste;
e. optionally, kneading of the paste.
18. Method according to one of Claims 11 to 17, comprising the features according
to one of Claims 1 to 10.
19. Electrode with improved ageing, obtained by the method according to one of
Claims 11 to 16.
20. Electrochemical supercapacitor comprising at least one electrode according to
Claim 19.

21. Use of a composition according to one of Claims 1 to 10 in the form of paste for
coating electrode collectors.

The invention relates to a composition that comprises a polymer binder and a catalytic compound which comprises
catalytic activated carbon and carbon nanotubes. The catalytic compound comprises carbon nanotubes obtained by chemical vapor
deposition of a hydrocarbon heated from 400 to 1100°C on activated carbon that has first been impregnated with a metal. The
invention also relates to the use of the compound as electrodes, of particular use in electrochemical double-layered energy storage
cells (supercapacitators). The invention is also aimed at the electrodes thus obtained and the supercapacitators containing these
compound materials, as well as the process for preparing electrodes with a catalytic compound containing activated carbon and
carbon nanotubes on a capacitator.