EP2223369A1 - Hybrid nanocomposite materials for hydrogen storage - Google Patents

Hybrid nanocomposite materials for hydrogen storage

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Publication number
EP2223369A1
EP2223369A1 EP08854854A EP08854854A EP2223369A1 EP 2223369 A1 EP2223369 A1 EP 2223369A1 EP 08854854 A EP08854854 A EP 08854854A EP 08854854 A EP08854854 A EP 08854854A EP 2223369 A1 EP2223369 A1 EP 2223369A1
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Prior art keywords
treating
solutions
nanocomposite material
preparation
carbon
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German (de)
French (fr)
Inventor
Maria Letizia Terranova
Massimiliano Lucci
Silvia Orlanducci
Francesco Toschi
Emanuela Tamburri
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0021—Carbon, e.g. active carbon, carbon nanotubes, fullerenes; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02—Polyamines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention concerns a new kind of materials for hydrogen storage and a process for their preparation.
  • the invention concerns hybrid nanocomposite materials for hydrogen storage, made of carbon nanostructures in a matrix made of a conductive polymer.
  • thermodynamics The main features required to the materials proposed for storing hydrogen are: - suitable adsorption and desorbing thermodynamics,
  • Main materials studied for hydrogen storage belong to five main classes: - metallic hydrides (A. Zuttel, Materials for hydrogen storage,
  • MOFs metal-organic frameworks
  • the class of metallic hydrides comprises a very high number of materials.
  • hydrides of intermetallic compounds give the best performances in terms of adsorbed hydrogen volumetric amount, while the percentage by weight ranges from 2 up to 10%. Nevertheless, desorption temperatures can be very high. Further, these materials are very heavy and can be easily polluted, and further they have high costs of production.
  • zeolites it is possible to operate at temperature and pressure conditions that are not too severe (temperatures of 20-200 0 C and pressures of 2-10MPa), but adsorbed hydrogen does not exceed 1.8%.
  • MOFs proposed as materials for hydrogen storage can adsorb hydrogen in an amount that is not higher than 4%, but only at very low temperature (77K).
  • PIMs polymer of intrinsic microporosity
  • the composition of these polymers can, in principal, be chemically varied and moduled. It is believed that adsorbing properties of these polymers exclusively depend on their microporosity. At present, using these polymers it is possible to reach an amount of adsorbed hydrogen of 2% by weight at 77K.
  • conductive polymers of the type of PANI (polyaniline) and PPY (polypirrole) proved to have a reversible adsorption ability of respectively 6% and 8% at environment temperature and pressure of 9,3MPa. Unfortunately, these results were not subsequently confirmed.
  • porous carbon materials raised a very high interest, thanks to the discover of nanostructured and/or nanometric carbon material such as nanotubes (CNT), nanofibres, fullerenes and nanoparticles.
  • nanostructured and/or nanometric carbon material such as nanotubes (CNT), nanofibres, fullerenes and nanoparticles.
  • nanocomposite materials In the formation of nanocomposite materials, the two components, generally known as matrix and filler, institute such relationships giving surprising features to the obtained material. For this reason the study and preparation of nanocomposite materials raised great scientific and technologic interest.
  • nanocomposites based on polymers and carbon nanotubes were successfully tested and used in mechanical, thermal and electronic applications. Storically, polymers always proved to act as inibitors with respect to gas adsorption because of the impossibility to reach micropores and/or their lack.
  • Conductive polymers and PIMs until now are the only materials that proved their ability in adsorbing hydrogen. Coupling these polymers with carbon nanometric materials, well known as gas adsorbing materials, can lead to the formation of extremely interesting nanocomposites.
  • Said materials are able to interact with gas, holding it in their interior and working in a range of temperature also comprising environment temperature, with storing time extremely fast in a range of pressure values also comprising environment pressure. Said materials are also capable of quickly releasing storaged hydrogen. Debonding times are in the range of one minute at environment temperature and even shorter if the system is heated, however always at a temperature lower than 100 0 C.
  • the aim of the present invention is therefore that of providing a new class of materials allowing to overcome the limits of the materials according to the prior art and to obtain the technical results previously described.
  • a further aim of the invention is that said materials can be realised with substantially limited costs.
  • a nanocomposite material for hydrogen storage made of a filler made of carbon nanostructures in a conductive polymeric matrix chosen amongst polyethylendioxytiophene (PEDOT), polypirrole (PPY), polyorthoanisydine (POA), polydiaminenaphthalenes (PDAN), polydiaminebenzenes (PDAB).
  • PEDOT polyethylendioxytiophene
  • PY polypirrole
  • POA polyorthoanisydine
  • PDAN polydiaminenaphthalenes
  • PDAB polydiaminebenzenes
  • said carbon nanostructures are chosen amongst: single wall carbon nanotubes (SWCNT), double wall carbon nanotubes (DWCNT), multiwall carbon nanotubes (MWCNT), nanowires and carbon nanofibres having a diametre shorter than 200 nm (NFC), carbon nanoparticles (amorphous or graphitic) having a diametre comprised between 10 and 500 nm (NPC), fullerenes (C 6 o).
  • SWCNT single wall carbon nanotubes
  • DWCNT double wall carbon nanotubes
  • MWCNT multiwall carbon nanotubes
  • NFC carbon nanoparticles (amorphous or graphitic) having a diametre comprised between 10 and 500 nm (NPC), fullerenes (C 6 o).
  • said carbon nanostructures are present in a concentration by weight comprised between 1% and 20% of the weight of the material.
  • said process further comprise a step, following the step of mixing between the polymer in solution and the nanometric material, of homogenising the polymer/nanomaterial dispersion in an ultrasound bath.
  • said process can further comprise a preliminar step of treatment of the carbon materials, chosen amongst:
  • said process for the preparation of a nanocomposite material provides for the use of electrochemical techniques with controlled potential, for the growing of each polymer. Further, according to the invention, said process provides for the use of solutions of monomers in concentration comprised between: 1mM and 10OmM and concentrations of carbon nanomaterial comprised between: 20 mg/l and 200 mg/l.
  • said process can further comprise a preliminar step of treatment of the carbon materials, chosen amongst:
  • said alternative process for the preparation of a nanocomposite material provides for the use of electrochemical techniques with controlled potential, for the growing of each polymer.
  • said further process provides for the use of solutions of monomers in concentration comprised between:
  • said process can further comprise a preliminar step of treatment of the carbon materials, chosen amongst:
  • Hybrid nanocomposite materials forming the object of the present invention have, with respect to the process of hydrogen storage/debonding, important advantages with regard to the single components constituting them. Further, such nanocomposites present a series of complimentary advantages typical of composite materials: - increased mechanical properties of the composite with respect to those of the polymer,
  • FIG. 1 shows a schematic view of the apparatus used for H 2 adsorption measures in the experimental tests made on some materials according to the present invention
  • - figures 2A and 2B show the quartzes of a microbalance respectively before and after the deposition of an adsorbing material according to the present invention
  • - figure 3 shows a photographic picture obtained with an optical microscope (con obiettivo 5Ox) of the film of polyethylendioxytiophene:polystirenesulphonate (PEDOTPSS) nanocomposite material with single wall carbon nanotubes (SWCNT), obtained according to the present invention
  • - figure 4 shows a photographic picture obtained with a scan electron microscope (SEM) of a polyethylendioxytiophene/single wall carbon nanotubes (PEDOT/SWCNT) nanocomposite material, obtained according to the present invention, wherein it is possible to see nanotubes in the polymeric matrix
  • - figure 5 shows a picture obtained with a STM microscope of a film of nanocomposite material based on polyorthoanisydine (POA) and multiwall carbon nanotubes (
  • - figure 6 shows examples of adsorption and desorption curves obtained at environment temperature and atmospheric pressure for films of nanocomposite material based on polyethylendioxytiophene:polystirenesulphonate and single wall carbon nanotubes treated in HNO 3
  • - figure 7 shows on a diagram the linear trend of the adsorption of the composite system polyorthoanisydine (POA) together with multiwall carbon nanotubes (MWCNT).
  • POA polyorthoanisydine
  • MWCNT multiwall carbon nanotubes
  • Hybrid nanocomposite material is made of an organic polymeric component belonging to the class of conductive polymers that can be chosen amongst the following: polyethylendioxytiophene (PEDOT), polypirrole (PPY), polyorthoanisydine (POA), polydiaminenaphthalenes (PDAN), polydiaminebenzenes (PDAB).
  • PEDOT polyethylendioxytiophene
  • PY polypirrole
  • POA polyorthoanisydine
  • PDAN polydiaminenaphthalenes
  • PDAB polydiaminebenzenes
  • the inorganic filler is a carbon nanometric material and can be chosen amongst the following: single wall carbon nanotubes (SWCNT), double wall carbon nanotubes (DWCNT), multiwall carbon nanotubes (MWCNT), nanowires and carbon nanofibres having a diametre shorter than 200 nm (NFC), carbon nanoparticles (amorphous or graphitic) having a diametre comprised between 10 and 500 nm (NPC), fullerenes (C 60 ).
  • SWCNT single wall carbon nanotubes
  • DWCNT double wall carbon nanotubes
  • MWCNT multiwall carbon nanotubes
  • NFC carbon nanofibres having a diametre shorter than 200 nm
  • NFC carbon nanoparticles (amorphous or graphitic) having a diametre comprised between 10 and 500 nm (NPC), fullerenes (C 60 ).
  • SWCNT SWCNT, DWCNT, MWCNT, NFC, NPC and C ⁇ o
  • SWCNT SWCNT, DWCNT, MWCNT, NFC, NPC and C ⁇ o
  • This method involves preparing a solution of polymer in a suitable solvent and its blending with a known amount of carbon nanomaterial.
  • the method provides for the use of an ultrasound bath, for homogenizing the polymer/nanomaterial dispersion.
  • the resulting nanocomposite can have concentrations by weight of carbon nanomaterial comprised between 1% and 20%.
  • the preparation of the nanocomposite material can be performed through electrochemical synthesis of the polymer with simultaneous inglobation of the nanometric material.
  • This method provides for the electrochemical deposititon of the polymer, starting from a solution of monomer in which carbon materials were dispersed.
  • electrochemical deposititon of the polymer starting from the monomer can be performed on a layer of nanocarbon materials previously deposited on the operating electrode.
  • the method provides for the electrochemical deposititon through the application of a suitable potential to the operating electrode.
  • the method provides for the use of electrochemical techniques with controlled potential. Potential is controlled to suitable values for the growing of each polymer.
  • Nanocomposite materials prepared according to one of the two different method previously shown, were subjected to the following determination hydrogen adsorption without further treatments and symulations. Hydrogen adsorption ,easure system
  • the method of preparation of the nanocomposite material through blending of the polymer in solution and the nanometric material provides for the deposition occurring directly on the device used for the determination of hydrogen adsorption.
  • Figure 1 shows a schematic view of the measuration device, in which the numeral 10 is used for an inert material room inside which a microbalance is positioned, and is respectfully linked to a H 2 c ylinder pointed as 11 and an inert gas cylinder 12, respectively through connecting lines on which fluximetres 13 are present. Fluximeters are controlled by a flux controller 14, operated by an electronic elaborator 15, to which data detected by the microbalance are conveyed after passage in a counter 16.
  • the measuration device used and shown in figure 1 worked at environment temperature. However, it is also possible to heat the system, in order to speed up the desorption step.
  • Adsorption/desorption measures shown in the following examples were performed in sequence, by measuring at first quartz alone, subsequently quartz on which adsorbing material was deposited and finally quartz with the adsorbing material after esposition to hydrogen. For the verification and quantification of hydrogen desorption it was proved that the mass of the sample decreased from time to time when subjected to a flux of an inert gas such as nitrogen, that is not adsorbed by the material in object.
  • an inert gas such as nitrogen
  • a solution was prepared comprised of 100ml of a polymer polyethylendioxytiophene:polystirenesulphonate (PEDOT.PSS) and a filler made of single wall carbon nanotubes (SWCNT), prelimina y treated with an acid solution of HNO 3 (150mg). An amount of 10 ⁇ l of this solution was deposited on the quartz surface used as microbalance (as shown in figures 2A and 2B). The system was maintained at 100 0 C for about 30 minutes.
  • Figure 3 shows a photografic pictuteres obtained with an optical microscope (5Ox magnifier) of the films of nanocomposite material prepared.
  • the sample was introduced in a measuration room made of inert material and was subjected for two hours to a nitrogen flux, to remove traces of other possible pollutants.
  • FIG. 6 shows on a diagram the adsorption and desorption curves obtained at environment temperature and atmospheric pressure. Diagram of figure 6 shows how the process is repeatible and completely reversible.
  • the amount of adsorbed hydrogen was of 4% by weight, with respect to the amount of filler (SWCNT) that is present in the nanocomposite material.
  • SWCNT filler
  • a solution was prepared comprised of a polymer PEDOTPSS
  • NPC (100ml) and 100mg of filler NPC.
  • the sample was introduced in the measurements rooms, inside which a flux of nitrogen was initially introduced, so to remove any traces of other possible pollutants. Subsequently, the sample was subjected to alternate flux hydrogen and nitrogen, so to verify the reversibility of the adsorption and desorption by means of an increase/decrease by weight.
  • the amount of adsorbed hydrogen measured with this system was of 3% by weight, with regard to the amount of filler intorduced in the nanocomposite.
  • a nanocomposite material made of PEDOT and SWCNT was prepared.
  • the sample was prepared through a synthesis/n situ, consisting in polymerisation starting from the respective monomer soluted in a solution wherein components of filler (SWCNT) to be included in the polymeric matrix were previously dispersed. Since this process of preparation is simply an electropolymerisation in acqueous mean, a preliminary treatment of SWCNT is necessary, so to introduce hydrophilic functions allowing the dispersion in the reaction means.
  • Figure 4 shows a photographic picture obtained with a scan electron microscope (SEM) of the nanocomposite material PEDOT/SWCNT. In the figure it is possible to see how the nanotubes link together different areas of the polymeric matrix.
  • SEM scan electron microscope
  • the electropolymerised sample was introduced in the measuration room and subjected for two hours at a flux of nitrogen, so to remove any traces of other possible pollutants.
  • the quartz covered by nanocomposite material was subjected to alternate fluxes of hydrogen and nitrogen, so to verify the reversibility of adsorption and desorption by means of an increase/decrease by weight.
  • the amount of adsorbed hydrogen of this system was comprised between 2 and 4% by weight with respect to the amount of filler introduced in the nanocomposite material.
  • a solution was prepared comprised of 100 ml of POA and 150 mg of filler of MWCNT.
  • Figure 5 shows a photographic picture obtained with a STM microscope of the films of nanocomposite material based on polyorthoanisydine (POA) and carbon nanotubes obtained. After drying, the sample was introduced in the measurement rooms made of inert material and was subjected for two hours at a flux of nitrogen, so to remove any traces of other possible pollutants.
  • POA polyorthoanisydine
  • the quartz covered by the nanocomposite material was subjected to alternate flux of hydrogen and nitrogen, so to verify the reversibility of the adsorption and desorption by means of an increase/decrease by weight.
  • Figure 7 shows the linear trend of the adsorption.
  • the amount of adsorbed hydrogen was 2-3% by weight with reference to the amount of filler (MWCNT) present in the nanocomposite material.
  • MWCNT filler

Abstract

The invention concerns a nanocomposite material for hydrogen storage, composed of a filler made of carbon nanostructures in a conductive polymeric matrix chosen amongst polyethylendioxytiophene (PEDOT), polypyrrole (PPY), polyorthoanisidine (POA), polydiaminenaphthalenes (PDAN), polydiaminebenzenes (PDAB). The invention further concerns processes for the preparation of said material.

Description

HYBRID NANOCOMPOSITE MATERIALS FOR HYDROGEN STORAGE
The present invention concerns a new kind of materials for hydrogen storage and a process for their preparation. In particular, the invention concerns hybrid nanocomposite materials for hydrogen storage, made of carbon nanostructures in a matrix made of a conductive polymer.
The search for innovative materials suitable for the storage of great amount of hydrogen is an objective of great importance. In fact, the capacity of storing great amounts of hydrogen is a crucial point for the development of technologies allowing for the use of hydrogen as automotive fuel or fuel for electric power generation, solution that could solve most of the problems of pollution in areas of high urbanization. Some international organizations, such as The United States Department of Energy (DOE), established an efficiency low threshold for storage systems and for sorption materials proposed as candidates for hydrogen storage (6,5% by weight).
The main features required to the materials proposed for storing hydrogen are: - suitable adsorption and desorbing thermodynamics,
- quick kinetics (for bonding and debonding),
- high storage capacity (high volumetric and gravimetric density),
- ability of efficiently transmitting heat,
- long life of adsorption/desorption cycles, - high mechanic strength of the material (and the container)
- safety in normal conditions and acceptable risk in non normal conditions.
Main materials studied for hydrogen storage belong to five main classes: - metallic hydrides (A. Zuttel, Materials for hydrogen storage,
Materials Today, 24-33, September 2003),
- metal-organic frameworks (MOFs)(N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M. O'Keeffe, O. M. Yaghi, Hydrogen storage in microporous metal-organic frameworks, Science, 300, 1127, 2003),
- zeolites (A. Zuttel, ibidem),
- polymers (Sung June Cho, Koyeon Choo, Dong Pyo Kim, Jong Won Kim, H2 sorption in HCI-treated polyaniline and polypyrrole, Catalysis Today 120 (2007) 336-340), (Colin D. Wood, Bien Tan, Abbie Trewin, Hongjun Niu, Darren Bradshaw.Matthew J. Rosseinsky, Yaroslav Z. Khimyak, Neil L. Campbell, Ralph Kirk.Ev Stδckel, and Andrew I. Cooper, Hydrogen Storage in Microporous Hypercrosslinked Organic Polymer Networks, Chem. Mater. 2007, 19, 2034-2048)
- porous carbon materials (W.-C. Xua, K. Takahashia,Y. Matsuoa,Y. Hattoria, M. Kumagaia, S. lshiyamab,K. Kanekoc, S. lijima, Investigation of hydrogen storage capacity of various carbon materials, International Journal of Hydrogen Energy, 32 (2007) 2504 - 2512) As it is also known, each of these materials presents merits, but also drawbacks, with reference to their use for hydrogen storage. Existing drawbacks hindered, until now, a large use or commercial development of these materials in the field in subject.
Problem generally affecting these materials are linked to the need for storing gas under particular conditions. In particular, specific needs of temperature (in general very low temperatures are needed, even hundreds of degrees under zero) and pressure (requested pressures are very high, even hundreds of atmospheres) must be respected.
On the other side, as far as gas debonding is concerned, it is often necessary to use very high temperature (even 400-8000C) in order to obtain a fast and complete debonding of the stored gas.
The class of metallic hydrides comprises a very high number of materials. At present, hydrides of intermetallic compounds give the best performances in terms of adsorbed hydrogen volumetric amount, while the percentage by weight ranges from 2 up to 10%. Nevertheless, desorption temperatures can be very high. Further, these materials are very heavy and can be easily polluted, and further they have high costs of production. In the case of zeolites, it is possible to operate at temperature and pressure conditions that are not too severe (temperatures of 20-2000C and pressures of 2-10MPa), but adsorbed hydrogen does not exceed 1.8%.
MOFs proposed as materials for hydrogen storage can adsorb hydrogen in an amount that is not higher than 4%, but only at very low temperature (77K).
Organic polymers called PIMs (polymer of intrinsic microporosity) proved to be effective in hydrogen adsorption. The composition of these polymers can, in principal, be chemically varied and moduled. It is believed that adsorbing properties of these polymers exclusively depend on their microporosity. At present, using these polymers it is possible to reach an amount of adsorbed hydrogen of 2% by weight at 77K.
According to some researches, conductive polymers of the type of PANI (polyaniline) and PPY (polypirrole) proved to have a reversible adsorption ability of respectively 6% and 8% at environment temperature and pressure of 9,3MPa. Unfortunately, these results were not subsequently confirmed. At present, it is believed that more realistic adsorption values for polyaniline are in the range of 0,1% at 500C and 60 bar and of 0,35% at 125°C and 60 bar (Michael Ulrich Jurczyka, Ashok Kumara, Sesha Srinivasanb, Elias Stefanakosb, Polyaniline-based nanocomposite materials for hydrogen storage, International Journal of Hydrogen Energy 32 (2007) 1010-1015) while no adsorption can be detected at environment temperature (Barbara Panella, Lina Kossykh, Ursula Dettlaff-Weglikowskab, Michael Hirscher, Giuseppe Zerbi, Siegmar Roth, Volumetric measurement of hydrogen storage in HCI-treated polyaniline and polypyrrole, Synthetic Metals 151 (2005) 208-210).
In recent years, porous carbon materials raised a very high interest, thanks to the discover of nanostructured and/or nanometric carbon material such as nanotubes (CNT), nanofibres, fullerenes and nanoparticles.
For carbon nanofibres hydrogen adsorption up to 60% was reported (Alan Chambers, Colin Park, R. Terry K. Baker, and Nelly M. Rodriguez, Hydrogen Storage in Graphite Nanofibers, J. Phys. Chem. B, Vol. 102, 4253, 1998). This result was never confirmed by other researches. More reliable and reproducible values of adsorption are comprised between 2 and 10% at environment temperature and pressure of 10 Mpa.
Resultats presented in literature, regarding carbon nanotubes, are extremely conflicting and strongly depend on the kind of nanotubes, the treatment they were subjected, the purity of the material and the presence of metallic polluters (Hui-Ming Cheng*, Quan-Hong Yang, Chang Liu, Hydrogen storage in carbon nanotubes, Carbon, 39 (2001), 1447 -1454). Published values range from 0,1 to 7% by weight.
Further, measures, taken by different laboratories, can be compared with difficulty because of the different samples preparation techniques and measure protocols used for determining the amount of adsorbed gas. The recent discover of polymeric materials capable to adsorb H2 paved the way to the preparation of innovative nanocomposite materials.
In the formation of nanocomposite materials, the two components, generally known as matrix and filler, institute such relationships giving surprising features to the obtained material. For this reason the study and preparation of nanocomposite materials raised great scientific and technologic interest. For example, nanocomposites based on polymers and carbon nanotubes were successfully tested and used in mechanical, thermal and electronic applications. Storically, polymers always proved to act as inibitors with respect to gas adsorption because of the impossibility to reach micropores and/or their lack. Conductive polymers and PIMs until now are the only materials that proved their ability in adsorbing hydrogen. Coupling these polymers with carbon nanometric materials, well known as gas adsorbing materials, can lead to the formation of extremely interesting nanocomposites. At present, results are known and published regarding only one research project regarding hydrogen adsorption by nanocomposite materials with a polymeric matrix and a filler made of carbon nanostructures. In particular, data relating to the adsorption on composite materials based on multiwall polyaniline/carbon nanotubes were published (Michael Ulrich Jurczyka, Ashok Kumara, Sesha Srinivasanb, Elias Stefanakosb, Polyaniline-based nanocomposite materials for hydrogen storage, International Journal of Hydrogen Energy, 32 (2007), 1010 - 1015), but values obtained for adsorption are not very promising. In this context is presented the solution according to the present invention, with the aim of providing for a new class of materials for hydrogen storage and a process for their preparation.
Said materials are able to interact with gas, holding it in their interior and working in a range of temperature also comprising environment temperature, with storing time extremely fast in a range of pressure values also comprising environment pressure. Said materials are also capable of quickly releasing storaged hydrogen. Debonding times are in the range of one minute at environment temperature and even shorter if the system is heated, however always at a temperature lower than 1000C. These and other results are obtained, according to the present invention, by proposing a new class of materials for hydrogen storage and a process for their preparation, said materials being nanocomposites, in which the matrix is a conductive polymer and the filler is a carbon nanometric material. The coupling of the two materials (conductive polymer as matrix, carbon nanomaterial as filler), according to the present invention, leads to the formation of a composite material with improved features of hydrogen adsorption with respect to the single constituents.
The aim of the present invention is therefore that of providing a new class of materials allowing to overcome the limits of the materials according to the prior art and to obtain the technical results previously described. A further aim of the invention is that said materials can be realised with substantially limited costs.
Not less aim of the invention is that of realising materials being substantially safe and reliable.
It is therefore a first specific object of the present invention a nanocomposite material for hydrogen storage, made of a filler made of carbon nanostructures in a conductive polymeric matrix chosen amongst polyethylendioxytiophene (PEDOT), polypirrole (PPY), polyorthoanisydine (POA), polydiaminenaphthalenes (PDAN), polydiaminebenzenes (PDAB). Preferably, according to the invention, said carbon nanostructures are chosen amongst: single wall carbon nanotubes (SWCNT), double wall carbon nanotubes (DWCNT), multiwall carbon nanotubes (MWCNT), nanowires and carbon nanofibres having a diametre shorter than 200 nm (NFC), carbon nanoparticles (amorphous or graphitic) having a diametre comprised between 10 and 500 nm (NPC), fullerenes (C6o). Further, always according to the invention, said carbon nanostructures are present in a concentration by weight comprised between 1% and 20% of the weight of the material.
It is further a second specific object of the present invention a process for the preparation of the nanocomposite material previously defined, comprising the following steps:
- preparing a solution of polymer in a suitable solvent,
- mixing between the polymer in solution and the nanometric material,
- solvent evaporation. Preferably according to the invention, said process further comprise a step, following the step of mixing between the polymer in solution and the nanometric material, of homogenising the polymer/nanomaterial dispersion in an ultrasound bath.
Further, still according to the invention, said process can further comprise a preliminar step of treatment of the carbon materials, chosen amongst:
- treating with acid solutions (HNO3 or H2SO4),
- treating with solutions made of acid mixtures HNO3/H2SO4,
- treating with basic solutions (KOH or NaOH),
- treating with solutions of H2O2, - treating with solutions made of mixtures of H2O2/H2SO4,
- thermal treating in oxidasing atmosphere at temperature comprised between 100 and 400 0C,
- treating with ultrasounds.
It is further a third specific object of the invention a alternative process for the preparation of the nanocomposite material previously defined, comprising the following steps:
- dispersing carbon materials in a solution of a monomer that is a precursor of the polymers, e
- electrochemical deposition of the dispersion through the application of a suitable potential to the operating electrode.
Preferably, according to the present invention, said process for the preparation of a nanocomposite material provides for the use of electrochemical techniques with controlled potential, for the growing of each polymer. Further, according to the invention, said process provides for the use of solutions of monomers in concentration comprised between: 1mM and 10OmM and concentrations of carbon nanomaterial comprised between: 20 mg/l and 200 mg/l.
Further, still according to the invention, said process can further comprise a preliminar step of treatment of the carbon materials, chosen amongst:
- treating with acid solutions (HNO3 or H2SO4),
- treating with solutions made of acid mixtures HNO3/H2SO4,
- treating with basic solutions (KOH or NaOH), - treating with solutions of H2O2,
- treating with solutions made of mixtures of H2O2ZH2SO4, - thermal treating in oxidasing atmosphere at temperature comprised between 100 and 400 0C,
- treating with ultrasounds.
It is further a fourth specific object of the invention a further alternative process for the preparation of the nanocomposite material previously defined, comprising the following steps:
- deposition of a layer of nanocarbon materials on an operative electrode,
- electrochemical deposition, from a solution of a monomer that is a precursor of the chosen polymer, through the application of a suitable potential to the operating electrode modified with the nanomaterial.
Preferably, according to the present invention, also said alternative process for the preparation of a nanocomposite material provides for the use of electrochemical techniques with controlled potential, for the growing of each polymer.
Further, according to the invention, said further process provides for the use of solutions of monomers in concentration comprised between:
1mM and 10OmM and concentrations of carbon nanomaterial comprised between: 20 mg/l and 200 mg/l. Still according to the invention, also said process can further comprise a preliminar step of treatment of the carbon materials, chosen amongst:
- treating with acid solutions (HNO3 or H2SO4),
- treating with solutions made of acid mixtures HNO3/H2SO4, - treating with basic solutions (KOH or NaOH),
- treating with solutions of H2O2,
- treating with solutions made of mixtures of H2O2/H2SO4,
- thermal treating in oxidasing atmosphere at temperature comprised between 100 and 400 0C, - treating with ultrasounds.
Hybrid nanocomposite materials forming the object of the present invention have, with respect to the process of hydrogen storage/debonding, important advantages with regard to the single components constituting them. Further, such nanocomposites present a series of complimentary advantages typical of composite materials: - increased mechanical properties of the composite with respect to those of the polymer,
- greater chemical inertia and greater resistance to chemical and atmospheric agents, - greater resistance to thermal decomposition,
- greater electric conducibility,
- smaller accumulation of electrostatic charges,
- better electromagnetic shielding in the field of radiowaves and microwaves. The present invention will now be described, for illustrative, non limitative purposes, according to its preferred embodiments, with particular reference to the following examples and to the figures of the enclosed drawings, wherein:
- figure 1 shows a schematic view of the apparatus used for H2 adsorption measures in the experimental tests made on some materials according to the present invention,
- figures 2A and 2B show the quartzes of a microbalance respectively before and after the deposition of an adsorbing material according to the present invention, - figure 3 shows a photographic picture obtained with an optical microscope (con obiettivo 5Ox) of the film of polyethylendioxytiophene:polystirenesulphonate (PEDOTPSS) nanocomposite material with single wall carbon nanotubes (SWCNT), obtained according to the present invention, - figure 4 shows a photographic picture obtained with a scan electron microscope (SEM) of a polyethylendioxytiophene/single wall carbon nanotubes (PEDOT/SWCNT) nanocomposite material, obtained according to the present invention, wherein it is possible to see nanotubes in the polymeric matrix, - figure 5 shows a picture obtained with a STM microscope of a film of nanocomposite material based on polyorthoanisydine (POA) and multiwall carbon nanotubes (MWCNT),
- figure 6 shows examples of adsorption and desorption curves obtained at environment temperature and atmospheric pressure for films of nanocomposite material based on polyethylendioxytiophene:polystirenesulphonate and single wall carbon nanotubes treated in HNO3, - figure 7 shows on a diagram the linear trend of the adsorption of the composite system polyorthoanisydine (POA) together with multiwall carbon nanotubes (MWCNT).
Preparation of hybrid nanocomposite materials Hybrid nanocomposite material is made of an organic polymeric component belonging to the class of conductive polymers that can be chosen amongst the following: polyethylendioxytiophene (PEDOT), polypirrole (PPY), polyorthoanisydine (POA), polydiaminenaphthalenes (PDAN), polydiaminebenzenes (PDAB). The inorganic filler is a carbon nanometric material and can be chosen amongst the following: single wall carbon nanotubes (SWCNT), double wall carbon nanotubes (DWCNT), multiwall carbon nanotubes (MWCNT), nanowires and carbon nanofibres having a diametre shorter than 200 nm (NFC), carbon nanoparticles (amorphous or graphitic) having a diametre comprised between 10 and 500 nm (NPC), fullerenes (C60).
The following carbon materials: SWCNT, DWCNT, MWCNT, NFC, NPC and Cδo can be used as such, or subjected to chemical or physical treatments as for example:
- treating with acid solutions (HNO3 or H2SO4), - treating with solutions made of acid mixtures HNO3/H2SO4,
- treating with basic solutions (KOH or NaOH),
- treating with solutions of H2O2,
- treating with solutions made of mixtures of H2O2/H2SO4,
- thermal treating in oxidasing atmosphere at temperature comprised between 100 and 400 0C,
- treating with ultrasounds.
In the following some preferred methods for the preparation of the nanocomposite material are shown.
According to a first method, it is possible to proceed through the blending of the polymer in solution and the nanometric material.
This method involves preparing a solution of polymer in a suitable solvent and its blending with a known amount of carbon nanomaterial.
Further, the method provides for the use of an ultrasound bath, for homogenizing the polymer/nanomaterial dispersion. After solvent evaporation, the resulting nanocomposite can have concentrations by weight of carbon nanomaterial comprised between 1% and 20%. As an alternative, the preparation of the nanocomposite material can be performed through electrochemical synthesis of the polymer with simultaneous inglobation of the nanometric material.
This method provides for the electrochemical deposititon of the polymer, starting from a solution of monomer in which carbon materials were dispersed. Alternatively, electrochemical deposititon of the polymer starting from the monomer can be performed on a layer of nanocarbon materials previously deposited on the operating electrode.
The method provides for the electrochemical deposititon through the application of a suitable potential to the operating electrode.
Further, the method provides for the use of electrochemical techniques with controlled potential. Potential is controlled to suitable values for the growing of each polymer.
Still, according to this method of preparation, it is provided for the use of solutions of monomers in concentration comprised between: 1mM and 10OmM and concentrations of carbon nanomaterial comprised between: 20 mg/l and 200 mg/l.
Nanocomposite materials, prepared according to one of the two different method previously shown, were subjected to the following determination hydrogen adsorption without further treatments and symulations. Hydrogen adsorption ,easure system
For determining the amount of adsorbed gaes it was developped an accurate and direct measurements system. The evaluation of samples of adsorbing material was made by means of a quartz microbalances
(Sauerbrey, G., Z. Phys. 155 (1959) 206-222) (K. O'Sullivan, G.G.
Guilbault, Review commercial quartz crystal microbalances — theory and applications, Biosens. Bioelectron. 14 (1999) 663-670). This technique, highly precise, provides for a very precise measure of the weight of a material placed in contsct with quarz.
According to this technique, hydrogen storage is detected and quantified by means of a ponderal increase of the material, while the subsequent desorption is detected by a corresponding ponderal decrease. For performing measures, microbilance is placed in a room, realised with inert material, to which a tube of inlet of the gas controlled by a flux controller is linked. According to the set experimental conditions, the sensitivity of measure results to be 2 ng. This apparatus was used for measuring the adsorption/desorption ability of composite materials prepared according to one of the two methods previously described.
The method of preparation of the nanocomposite material through blending of the polymer in solution and the nanometric material provides for the deposition occurring directly on the device used for the determination of hydrogen adsorption.
The method of preparation of the nanocomposite material through electrochemical synthesis of the polymer, with simultaneous inglobation of the nanometric material, provided for the deposition to occur on an electrode, subsequently used directly on the system fo hydrogen adsorption determination.
Figure 1 shows a schematic view of the measuration device, in which the numeral 10 is used for an inert material room inside which a microbalance is positioned, and is respectfully linked to a H2 c ylinder pointed as 11 and an inert gas cylinder 12, respectively through connecting lines on which fluximetres 13 are present. Fluximeters are controlled by a flux controller 14, operated by an electronic elaborator 15, to which data detected by the microbalance are conveyed after passage in a counter 16.
The measuration device used and shown in figure 1 worked at environment temperature. However, it is also possible to heat the system, in order to speed up the desorption step.
All the measures reported hereinafter were taken at environments T and atmospheric pressure.
Adsorption/desorption measures shown in the following examples were performed in sequence, by measuring at first quartz alone, subsequently quartz on which adsorbing material was deposited and finally quartz with the adsorbing material after esposition to hydrogen. For the verification and quantification of hydrogen desorption it was proved that the mass of the sample decreased from time to time when subjected to a flux of an inert gas such as nitrogen, that is not adsorbed by the material in object.
On the same materials, further measures were performed with conventional polmonation-desorption method. Such measures showed mass (%) adsorption values that can be compared with the values obtained using the microbalance. In the following some examples of preparation of materials according to the present invention are shown. Example 1
A solution was prepared comprised of 100ml of a polymer polyethylendioxytiophene:polystirenesulphonate (PEDOT.PSS) and a filler made of single wall carbon nanotubes (SWCNT), prelimina y treated with an acid solution of HNO3 (150mg). An amount of 10 μl of this solution was deposited on the quartz surface used as microbalance (as shown in figures 2A and 2B). The system was maintained at 1000C for about 30 minutes. Figure 3 shows a photografic pictuteres obtained with an optical microscope (5Ox magnifier) of the films of nanocomposite material prepared.
Subsequently, the sample was introduced in a measuration room made of inert material and was subjected for two hours to a nitrogen flux, to remove traces of other possible pollutants.
Once the cleaning step is finished, the quartz covered with nanocomposite material was subjected to alternate fluxes of hydrogen and nitrogen, so to verify the reversibility of adsorption and desorption through an increase/decrease of weight. Figure 6 shows on a diagram the adsorption and desorption curves obtained at environment temperature and atmospheric pressure. Diagram of figure 6 shows how the process is repeatible and completely reversible.
The amount of adsorbed hydrogen was of 4% by weight, with respect to the amount of filler (SWCNT) that is present in the nanocomposite material. Example 2
A solution was prepared comprised of a polymer PEDOTPSS
(100ml) and 100mg of filler NPC. NPC were preliminarly treated with a basic solution of KOH 1OM for 2 hours, the dispersion was performed at values of pH=7 through wash with distilled water and and after brought to dry, in an oven at a temperature of 80°C.
Subsequently, 15 μl of the solution of PEDOT.'PSS and NP were deposited on the surface of a quartz used as microbalance (of the tyoe shown with reference to Fig. 2). The system was amintained at 1000C for about 30 minutes.
Subsequently, the sample was introduced in the measurements rooms, inside which a flux of nitrogen was initially introduced, so to remove any traces of other possible pollutants. Subsequently, the sample was subjected to alternate flux hydrogen and nitrogen, so to verify the reversibility of the adsorption and desorption by means of an increase/decrease by weight. The amount of adsorbed hydrogen measured with this system was of 3% by weight, with regard to the amount of filler intorduced in the nanocomposite. Example 3
Using an electropolymerisation process, a nanocomposite material made of PEDOT and SWCNT was prepared. The sample was prepared through a synthesis/n situ, consisting in polymerisation starting from the respective monomer soluted in a solution wherein components of filler (SWCNT) to be included in the polymeric matrix were previously dispersed. Since this process of preparation is simply an electropolymerisation in acqueous mean, a preliminary treatment of SWCNT is necessary, so to introduce hydrophilic functions allowing the dispersion in the reaction means.
As a consequence, 200 mg of SWCNT were treated with a mixture of HNO3:H2SO4 in a ratio 3:1 for 1h, therefore the solution was at a pH=6,5 through washing with distilled water and subsequently made dry by treating with an oven at 800C. An amount of 3 mg of treated SWCNT was dispersed in acqueous solution through sonication. The dispersion had a concentration of 10 mM of monomer ethylendioxytiophene (EDOT) and 0,1mM of electrolite NaPSS. The composite material was deposited through application of a potential of 1 ,25V versus the reference potential of the Ag/AgCI electrode on the surface of a quartz used as microbalance, previously put in contact with a suitable potentiostat.
Figure 4 shows a photographic picture obtained with a scan electron microscope (SEM) of the nanocomposite material PEDOT/SWCNT. In the figure it is possible to see how the nanotubes link together different areas of the polymeric matrix.
The electropolymerised sample was introduced in the measuration room and subjected for two hours at a flux of nitrogen, so to remove any traces of other possible pollutants. When the cleaning step is ended, the quartz covered by nanocomposite material was subjected to alternate fluxes of hydrogen and nitrogen, so to verify the reversibility of adsorption and desorption by means of an increase/decrease by weight. The amount of adsorbed hydrogen of this system was comprised between 2 and 4% by weight with respect to the amount of filler introduced in the nanocomposite material. Example 4
A solution was prepared comprised of 100 ml of POA and 150 mg of filler of MWCNT. The multiwall carbon nanotubes (MWCNT) were previously treated with an acid solution of H2SO4 5M for 2 h, the solution was brought to pH=7 by means of repeated washing with distilled water.
The solution was then maintained in an oven at 80 0C for 1 h.
An amount of 10 μl of this solution was deposited on the surface of a quartz used as microbalance (in the way shown with reference to figure 2A and 2B). The system was kept at 1000C for about 30 minutes.
Figure 5 shows a photographic picture obtained with a STM microscope of the films of nanocomposite material based on polyorthoanisydine (POA) and carbon nanotubes obtained. After drying, the sample was introduced in the measurement rooms made of inert material and was subjected for two hours at a flux of nitrogen, so to remove any traces of other possible pollutants.
When the cleaning step was ended, the quartz covered by the nanocomposite material was subjected to alternate flux of hydrogen and nitrogen, so to verify the reversibility of the adsorption and desorption by means of an increase/decrease by weight. Figure 7 shows the linear trend of the adsorption. The amount of adsorbed hydrogen was 2-3% by weight with reference to the amount of filler (MWCNT) present in the nanocomposite material. The present invention was described for illustrative, non limitative purposes, according to its preferred embodiments, but it is to be understood that any variation and/or modification can be made by those skilled in the art without for this reason escaping the relative scope of protection, as defined in the enclosed claims.

Claims

1. Nanocomposite material for hydrogen storage, characterised in that it is composed of a filler made of carbon nanostructures in a conductive polymeric matrix chosen amongst polyethylendioxytiophene (PEDOT), polypirrole (PPY), polyorthoanisydine
(POA), polydiaminenaphthalenes (PDAN), polydiaminebenzenes (PDAB).
2. Nanocomposite material according to claim 1 , characterised in that said carbon nanostructures are chosen amongst: single wall carbon nanotubes (SWCNT), double wall carbon nanotubes (DWCNT), multiwal! carbon nanotubes (MWCNT), nanowires and carbon nanofibres having a diametre shorter than 200 nm (NFC), carbon nanoparticles (amorphous or graphitic) having a diametre comprised between 10 and 500 nm (NPC), fullerenes (C60).
3. Nanocomposite material according to claim 1 or 2, characterised in that said carbon nanostructures are present in a concentration by weight comprised between 1% and 20% of the weight of the material.
4. Process for the preparation of the nanocomposite material as defined in claims 1-3, characterised by comprising the following steps: - preparing a solution of polymer in a suitable solvent,
- mixing between the polymer in solution and the nanometric material,
- solvent evaporation.
5. Process for the preparation of a nanocomposite material according to claim 4, characterised in that it further comprises a step, following the step of mixing between the polymer in solution and the nanometric material, of homogenising the polymer/nanomaterial dispersion in an ultrasound bath.
6. Process for the preparation of a nanocomposite material according to any of claims 4 or 5, characterised in that it further comprises a preliminar step of treatment of the carbon materials, chosen amongst:
- treating with acid solutions (HNO3 or HZSO4),
- treating with solutions made of acid mixtures HNO3/H2SO4,
- treating with basic solutions (KOH or NaOH), - treating with solutions of H2O2,
- treating with solutions made of mixtures of H2O2/H2SO4, - thermal treating in oxidasing atmosphere at temperature comprised between 100 and 400 °C,
- treating with ultrasounds.
7. Process for the preparation of the nanocomposite material as defined in claims 1-3, characterised by comprising the following steps:
- dispersion carbon materials in a solution of a monomer that is a precursor of the polymers, and
- electrochemical deposititon of the dispersion through the application of a suitable potential to the operating electrode.
8. Process for the preparation of a nanocomposite material according to claim 7, characterised in that it provides for the use of electrochemical techniques with controlled potential, for the growing of each polymer.
9. Process for the preparation of a nanocomposite material according to claim 7 or 8, characterised in that it provides for the use of solutions of monomers in concentration comprised between: 1mM and 10OmM and concentrations of carbon nanomaterial comprised between: 20 mg/l and 200 mg/l.
10. Process for the preparation of a nanocomposite material according to any of claims 7-9, characterised in that it further comprises a preliminary step of treatment of the carbon materials, chosen amongst:
- treating with acid solutions (HNO3 or H2SO4),
- treating with solutions made of acid mixtures HNO3/H2SO4,
- treating with basic solutions (KOH or NaOH), - treating with solutions of H2O2,
- treating with solutions made of mixtures of H2O2ZH2SO4,
- thermal treating in oxidasing atmosphere at temperature comprised between 100 and 400 0C,
- treating with ultrasounds.
11. Process for the preparation of the nanocomposite material as defined in claims 1-3, characterised by comprising the following steps:
- deposition of a layer of nanocarbon materials on an operative electrode,
- electrochemical deposititon from a solution of a monomer that is a precursor of the chosen polymer through the application of a suitable potential to the operating electrode modified with the nanomaterial.
12. Process for the preparation of a nanocomposite material according to claim 11, characterised in that it provides for the use of electrochemical techniques with controlled potential, for the growing of each polymer.
13. Process for the preparation of a nanocomposite material according to claim 11 or 12, characterised in that it provides for the use of solutions of monomers in concentration comprised between: 1mM and 10OmM and concentrations of carbon nanomaterial comprised between: 20 mg/l and 200 mg/l.
14. Process for the preparation of a nanocomposite material according to any of claims 11 - 13, characterised in that it further comprises a preliminary step of treatment of the carbon materials, chosen amongst:
- treating with acid solutions (HNO3 or H2SO4),
- treating with solutions made of acid mixtures HNO3/H2SO4, - treating with basic solutions (KOH or NaOH),
- treating with solutions of H2O2,
- treating with solutions made of mixtures of H2O2/H2SO4,
- thermal treating in oxidasing atmosphere at temperature comprised between 100 and 400 0C, - treating with ultrasounds.
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