Proton conductor, its production process, and electrochemical device using it

FIELD: electrical engineering; proton conductors, their production, and electrochemical devices using them.

SUBSTANCE: proposed proton (H+)conductor has carbonic material essentially composed of carbon and proton dissociation groups introduced therein. Protons are moving in this proton conductor between proton dissociation groups. Ion conductance of proton conductor is higher than its electron conductance. Carbonic materials used for the purpose are carbon clusters, such as fullerene or carbonic tubular material, or so-called carbonic nanotubes having diamond-shaped structure. This conductor can be used in the form of thin film within wide temperature range at any humidity.

EFFECT: reduced size and simplified design of electrochemical device.

56 cl, 30 dwg, 3 tbl, 12 ex

 

The present invention relates to a proton (H+) conductor, method thereof, and electrochemical device using it.

The prior art fuel cell used as an energy source for vehicles based on solid polymer electrolyte, in which the applied polymeric material having a proton (ion-hydrogen) electrical conductivity, such as perversionen resin (e.g., Nation ®manufactured by Du Pont).

As a relatively new proton conductor also known polymolybdates having a large number of hydrated water, such as H3Mo12PO40·29N2O, or an oxide having a large number of hydrated water, such as Sb2O6·5,4H2O. Each of the above compounds - polymer material and hydrated compounds, being placed in a moist condition, exhibit high proton conductivity at a temperature close to normal ambient temperature.

For example, the reason that perversionen resin can exhibit very high proton conductivity even at ordinary temperature, is that the protons ionized from the sulphonate groups of the resin, are connected (through hydrogen bonding) with moisture, which already zachvac the polymer matrix in large quantities, resulting protonated water, that is of hydronium ions (H3About+), and the protons in the form of hydronium ions can move easily in the polymer matrix.

Recently also developed a proton conductor having a conductivity mechanism different from that described for each of the above proton conductors.

It is established that the composite metal oxide having perovskite structure, such as SrCeO3with additive Yb, shows proton conductivity without the use of moisture as migration environment. Suppose that the mechanism of conductivity of this composite metal oxide is that, being channeled, the protons are conducted one by one between the oxygen ions, forming the skeleton perovskite structure.

However, conducting protons were not originally present in the composite metal oxide, and the result of the following mechanism. When perovskite structure is in contact with the vapor contained in the ambient atmospheric air, the water molecules at high temperature react with parts having an oxygen deficiency, which was formed in perovskite structure by doping with Yb or the like additives, resulting in formation of protons.

However, the above proton the e conductors have the following disadvantages.

The matrix material such as the aforementioned perversionen resin during its use must always be in a sufficiently wet state, to maintain high proton conductivity.

Accordingly, the configuration of the system, such as a fuel cell using such a matrix material, requires a humidifier and various assistive devices that entails increasing the size of the system and increasing the cost of the system.

A system using such a matrix material, also has the disadvantage that the operating temperature range must be limited in order to prevent freezing or evaporating moisture contained in the matrix.

When using a composite metal oxide having perovskite structure, the problem arises of ensuring the effective proton conductivity. For this purpose it is necessary to maintain a high operating temperature, which is about 500°C.

Thus, known from the existing state of the art proton conductors have drawbacks lies in their high dependence on atmospheric conditions, so as to ensure the work of the conductor it is necessary to apply moisture or air flow. In addition, the working temperature of the conductor is extremely high or u is n operating temperature is limited.

The present invention is the task to create a proton conductor, which can be used in a wide temperature range including normal environmental temperature, which did not depend on atmospheric conditions, working, regardless of whether there is or there is moisture in the migration environment, i.e. not requiring the filing of moisture, and also to create a way of obtaining such a proton conductor and electrochemical device that uses this proton conductor.

Another objective behind the present invention is to provide a proton conductor, which would have the ability education film, while maintaining the above-described characteristics, so that it could be used in the form of a thin film having high durability and capable of preventing the penetration of gases, or proof, as well as having good proton conductivity, and a method of obtaining such a proton conductor, and an electrochemical device that uses this proton conductor.

The present invention provides for the creation of a proton conductor that includes a carbonaceous material, essentially consisting of carbon, which introduced the group to the dissociation of protons.

The present invention also provides the method according to the teachings of the proton conductor, including the stage of introduction of the groups to the dissociation of protons in the carbonaceous material, essentially consisting of carbon.

The present invention relates to electrochemical devices comprising the first electrode, the second electrode, and a proton conductor located between the first and second electrodes, and a proton conductor includes a carbon material, essentially consisting of carbon, which introduced the group to the dissociation of protons.

The proton conductor of the present invention, since the conductor is essentially composed of a carbon material that is capable of dissociation of protons, characterized by the fact that protons are easily transferred or easily carried out, even in the dry state, and in addition, the protons may exhibit high conductivity in a wide temperature range (at least in the range from about -40°160° (C)that includes a normal temperature. The proton conductor of the present invention has a sufficient proton conductivity even in a dry condition. He also has a proton conductivity in the wet state. Moisture can come from outside.

The electrochemical device of the present invention, since the proton conductor is located between the first and second electrodes, characterized by the fact that it electromechani is a mini device can eliminate the need for the humidifier and the like, which are necessary for the well-known fuel cells, which are to improve proton conductivity require moisture as migration environment. Thus, the device of the present invention has advantages consisting in a reduced size and simplified design.

The characteristics and advantages of the present invention will be clear from the following description, which is conducted with reference to the figures of drawings, on which:

figa and 1B depict the structure of the molecule polyhydroxyalkane fullerene, as one of the examples of the fullerene derivatives of the present invention;

figa, 2B and 2C are examples of derivatives of fullerene, which introduced the group to the dissociation of protons;

figa and 3B are examples of the fullerene molecules;

figure 4 - examples of carbon clusters, which is essentially a proton conductor according to the present invention;

5 - other examples of carbon clusters, which have partial fullerene structure;

6 - other examples of carbon clusters, which have the structure of diamond.

7 - additional examples of carbon clusters, which are connected with each other;

Fig - schematically an example of a proton conductor according to the present invention;

Fig.9 is a schematic configuration of the fuel element;

figure 10 - schemacachingduration hydrogen-air element;

11 is a schematic depiction of the configuration of the electrochemical device;

Fig - schematically the configuration of another electrochemical device;

each of figa and 13B depicts examples of tubular carbon materials of the present invention as a source or raw materials for proton conductor of the present invention;

Fig - derived tubular carbonaceous material according to the present invention;

Fig is schematically derived tubular carbonaceous material;

Fig is schematically another derivative of the tubular carbonaceous material;

figa and 17B diagrams of equivalent circuits of the experimental tablets, used in the exemplary embodiment of the present invention;

Fig is a graph showing the measurement result of the impedance tablets in complex form;

Fig is a graph showing the dependence of the proton conductivity of tablets on temperature;

Fig is a graph showing the results of an experiment on generation of electricity using fullerene derivative described in example 1 implementation of the present invention;

Fig is a graph showing the measurement result of the impedance in the complex form of tablets in example 4 of the present invention and tablets used in the comparative is m example 2;

Fig is a graph showing the dependence of the proton conductivity of tablets on temperature;

Fig is a graph showing the TOF-MS spectrum of the carbon powder obtained by the method of arc discharge using carbon conductor in example 8 of the present invention; and

Fig is a graph showing the measurement of complex impedance of film used in the embodiment of the present invention, in which applied the tubular carbonaceous material.

Below details the proton conductor and method for producing the proton conductor to which is applied the present invention, and electrochemical device using the proton conductor, with reference to the accompanying figures of the drawings.

The proton conductor according to one of the embodiments of the present invention includes a carbon material, essentially consisting of carbon, which introduced the group to the dissociation of protons. In the present description "the dissociation of a proton (H+)" means "the dissociation of a proton from the functional groups in response to ionization"and "group dissociation of protons" refers to a functional group capable of transporting protons in response to ionization".

In such a proton conductor protons are forced to move between groups is the dissociation of protons, as a result they exhibit ionic conductivity.

As a fullerene derivative, you can use any suitable material, provided that it consists mainly of carbon. However, it is necessary that after the introduction of the groups to the dissociation of protons ionic conductivity was higher than the electronic conductivity.

Derivative of fullerene, as a matrix fullerene derivative, specifically, can be represented by carbon clusters as units of carbon atoms, and the carbon material containing diamond structure.

There are various carbon clusters. Of them fullerene, fullerene structure at least part of which has an open end, and carbon tubular material, or so-called carbon nanotubes, are preferred.

These materials, of course, are only as illustrations, as appropriate, is any material which satisfies the above conditions, namely, that the ionic conductivity after the introduction of the groups to the dissociation of protons was higher than the electronic conductivity.

Below describes some typical applications of the present invention to those given as examples of the carbon materials.

First, describes an example of using fullerene as a carbon material.

In the accordance with this embodiment of the invention, the type of molecule or molecules of the fullerene used as source material for the derivative of fullerene, which introduced the group to the dissociation of protons, is not specifically limited, provided that the fullerene molecule are characterized as spherical carbon clusters or carbon clusters, which are mainly comprised of fullerene molecule With36C60(see figa)70(see figv)76With78With80C82and C84. It should be noted that, as a starting material to obtain a fullerene derivative can also be used a mixture of these fullerene molecules such as fullerene molecules.

The fullerene molecule was found in the mass spectrum of the beam of the carbon cluster, obtained by laser resurfacing graphite in 1985 (H.W. Kroto, J.R. Heath, S.C. O'brien, R.F. Curl and R.E. Smalley, Nature, (1985), 318, 162).

The method of producing fullerene molecules using arc discharge carbon electrode was developed five years later, in 1990. With design-time actionable ways to produce a fullerene molecule located in the centre of attention in connection with the use as a carbon-based semiconductor material or a similar material.

The authors of the present invention for the first time since obtaining useful results investigated the proton conductivity of p is ossadnik these fullerene molecules and installed, what polyhydroxyalkane fullerene obtained by introducing hydroxyl groups to the number of carbon atoms of a molecule or molecules of the fullerene, shows, even in the dry state, high proton conductivity in a wide temperature range, including in the area of normal temperature, i.e. the temperature range from a temperature below the freezing point of water to temperatures above the boiling point of water (at least from -40°160° (C), and also found that the proton conductivity becomes higher when a molecule or molecules of the fullerene entered hydrosulphate ester groups, namely group -OSO3N, instead of hydroxyl groups.

More specifically, polyhydroxyalkane fullerene or fullerene is the generic name is based on fullerene compounds having a structure in which the molecule or molecules of the fullerene added many hydroxyl groups, as shown in figures 1A and 1B. Of course, there may be some variations in the number, location and other characteristics of the hydroxyl groups of fullerene molecules. An example of the first synthesis polyhydroxyalkane fullerene described by Chiang and others in 1992 (L.Y. Chiang, J.W. Swirczewski, C.S. Hsu, S.K. Chowdhury, S. Cameron and K. Creengan, J. Chem. Soc., Chem. Commun., (1992), 1791). After this message polyhydroxyalkane fullerene containing a specified or more of hydroc the ilen groups, began to be in the spotlight, in particular, for its ability to dissolve in water, and studied mainly in the field of biotechnology.

In the implementation of one embodiment of the present invention, it was found that fullerene derivative may be formed from an aggregation of molecules polyhydroxyalkane fullerene, as schematically shown in figa, in which the hydroxyl group of each of these molecules adjacent to each other (this figure is About refers to a molecule polyhydroxyalkane fullerene), interact with each other, resulting in a high proton conductivity (i.e. high ability to transfer N+between phenolic hydroxyl groups in the molecule or molecules polyhydroxyalkane fullerene), within the mixture or aggregate of molecules polyhydroxyalkane fullerene.

In this embodiment of the invention, the proton conductor can be used in the Assembly of fullerene molecules, where each molecule or several molecules have many groups-OSO3N, instead of an Assembly of molecules polyhydroxyalkane fullerene described above. About based on the fullerene compound, in which group HE substituted groups-OSO3N, as shown in figv, i.e. the hydrosulfate-esterified fullerenol (polyhydroxy-hydrosulfate the bath fullerene) reported Chiang and others in 1994 (L.Y. Chiang, L.Y. Wang, J.W. Swirczewski, S. Soled and S. Cameron, J. Organ Chem., 59, 3960 (1994)). Molecules polyhydroxy-hydrosulfurous fullerene can only contain group-OSO3N or contain a number of groups-OSO3N and the number of hydroxyl groups.

In the case of obtaining fullerene derivative of the present invention receive a unit consisting of a large number of molecules of the fullerene derivative containing a hydroxyl group or group-OSO3N, or combinations thereof. Because the protons originating from a large number of hydroxyl groups or groups-OSO3N or combinations thereof, which was initially contained in the molecules migrate directly, the proton conductivity of the mixture or aggregate of such fullerene molecules occurs by itself, without the need for capture of hydrogen originating from the vapor molecules, or photons from the atmosphere, and also without the need of water inflow from the surrounding environment, in particular without the need of absorption of water or the like from atmospheric air. In other words, the proton conductivity of the Assembly of molecules of fullerene derivative containing the functional group is not limited by the atmospheric environment.

In addition, the fullerene molecule as starting material to obtain the derivatives of fullerene, in particular, possess electrophilic the properties, due to which not only the group-OSO3N, with high acidity, but also hydroxyl groups can largely facilitate the ionization of hydrogen. This is one of the reasons that the proton conductor according to one of the embodiments of the present invention shows excellent proton conductivity.

In accordance with the proton conductor according to one of the embodiments of the present invention, since a large number of hydroxyl groups or groups-OSO3N or their combinations can be entered in each of the molecules or the number of molecules of the fullerene derivative, the value of the density of protons associated with the conductivity per unit volume of the conductor becomes very large. This is another reason that the proton conductor according to this variant implementation of the present invention demonstrates effective conductivity.

Because the molecule or molecules of the fullerene derivative of the proton conductor according to this variant implementation of the present invention mainly or essentially consist of carbon atoms, it fullerene derivative has a low weight, is difficult to decomposition and relatively clean, i.e. relatively free of impurities that would adversely affect the desired properties of the proton conductivity. In addition, cost is, necessary to obtain this derivative of fullerene, are greatly reduced. On this basis, it fullerene derivative can be viewed as the desired carbonaceous material, based on available resources, environmental conditions, economic conditions and other characteristics, as reported above.

As a result of this invention it was also found that the groups described above dissociation of protons are not limited to, functional groups, representing only a hydroxyl group or group-OSO3N.

More specifically, the group dissociation of protons can be expressed by a chemical formula XH, where X represents any atom or atomic group having a bivalent connection, and in addition, this group can be expressed by a chemical formula HE or YOH, where Y is any atom or atomic group having a bivalent connection.

In particular, the group dissociation of protons preferably represent at least one of the functional groups-HE-OSO3H and-COOH, -SO3N-ORO(OH)3.

In accordance with this embodiment of the present invention, attracts electrons, such as nitro, carbonyl groups and carboxyl groups, nitrile groups, alkylhalogenide groups or halogen atoms (atoms FPO is a or chlorine) can preferably be introduced, together with the dissociation of protons in the carbon atoms of the molecule or molecules of the fullerene. On figs shows the fullerene molecule, which in addition to HE introduced the group Z, where Z represents at least one of the following groups, attracts electrons: -NO2, -CN, -F, -CL, -COOR, -Cho, -COR, -CF3or-SO3CF3(R represents an alkyl group). If there are groups that attracts electrons, in addition to the functional groups, protons, it can easily be removed from groups dissociation of protons and transferred between functional groups due to the effect of electron attraction groups, attracts electrons.

In accordance with this embodiment of the invention it is possible to arbitrarily choose the number of groups to the dissociation of protons, provided that it is smaller than the number of carbon atoms of a molecule or molecules of the fullerene, and preferably it may include 5 or more functional groups. To maintain π-electronic characteristics of the fullerene molecule level, allowing to acquire the property of the effective attraction of the electrons, the number of functional groups is more preferable should be half or less than half the number of carbon atoms of a molecule or molecules of the fullerene.

To synthesize the above-described fullerene derivative used as a proton conductor in one embodiment of the present invention, as bodø is described below with reference to examples, the desired group to the dissociation of protons can be introduced into the carbon atoms of each molecule or several molecules of the fullerene derivative, subjecting the powder consisting of fullerene molecules, known processing methods, such as acid treatment and hydrolysis, or a combination of these treatments.

After processing, the powder thus obtained fullerene derivative can be sealed, shaping the product desired form, for example tablets. The powder densification can be carried out without use of any binder, which is important to improve proton conductivity and reduced mass of the proton conductor and allows to obtain a molded material, essentially consisting of a fullerene derivative.

The proton conductor according to this variant embodiment of the invention is useful for various electrochemical devices. For example, the present invention can preferably be applied to an electrochemical device having a basic structure comprising first and second electrodes and located between the proton conductor, and this proton conductor has a configuration of a proton conductor according to the present invention.

More specifically, the proton conductor according to this variant embodiment of the invention preferably can be used to electrochim the ical device, in which at least one of the first and second electrodes is a gas electrode, or for electrochemical devices, and in which at least one of the first and the second electrode is an active electrode.

Below is an example in which the proton conductor according to this variant embodiment of the invention is used in a fuel cell.

Fig depicts schematically the proton conductivity of the fuel element, which conducts protons part 1 is located between the first electrode 2 (for example, a hydrogen electrode and the second electrode 3 (for example, an oxygen electrode), and protons, dissociatively or moved in conducting protons part 1 migrate from the first electrode 2 toward the second electrode 3 in the direction shown by the arrow on Fig.

Fig.9 depicts schematically a specific example of a fuel cell, which uses a proton conductor according to this variant embodiment of the invention. The fuel element is designed so that the first negative electrode 2 (fuel electrode or hydrogen electrode), which is closely adjacent or in which the dispersed catalyst 2A and which has a terminal 8, is located opposite the second positive electrode 3 (oxygen electrode), which is close note what appears or in which the dispersed catalyst 3A and which has a terminal 9, and between them is a conductive protons part 1. When using a fuel cell, hydrogen is supplied from the inlet 12 to the negative side of the first electrode 2 into the channel 15 and out of the outlet 13 (which is sometimes not available) on the negative side of the first electrode 2. The protons formed during the period when the fuel (H2) 14 passes through the channel 15. These protons move with the protons formed in the conductive protons, part 1, on the positive side of the second electrode 3 and react with oxygen (air) 19, which is fed into the channel 17 of the inlet 16 and moves in the direction to release 18, and this creates the desired electromotive force.

In a fuel cell having the above configuration, since the protons formed in the conductive protons, part 1, move with the protons coming from the negative side of the first electrode 2 on the side of the second positive electrode 3, the proton conductivity increases. This eliminates the need for any moisturizer or other source of water or other external migration environment, and thereby simplifies the system configuration and the reduced mass of the system.

Another variant of implementation of the present invention is described below. Another option is the implementation of this is subramania differs from the above to the exercise of the option, that the above-described fullerene derivative is used in combination with a polymeric material. However, the proton conductor according to the second variant of implementation of the present invention has essentially the same characteristics proton conductivity, as described in the above embodiment of the invention.

The second proton conductor in this embodiment of the invention contains the above-described fullerene derivative (which introduced the group to the dissociation of protons, namely the carbon atoms constituting the fullerene and polymer material.

The polymeric material may consist of one species or two or more kinds of known polymers having film-forming ability. The content of the polymer material is usually 50 wt.% or less. If this content is higher than 50 wt.%, the proton conductivity of the fullerene derivative may be reduced.

Because the second proton conductor in this embodiment of the present invention contains a derivative of fullerene, it can exhibit proton conductivity comparable to the rate of the proton conductor of the present invention.

While the proton conductor according to the present variant embodiment of the invention, containing only the fullerene derivative used in the form of a compacted powder, the AK described above, the second proton conductor in this embodiment of the invention, having the property of film formation obtained from a polymeric material, can be used as a flexible thin conducting protons films possessing great strength and gas impermeability. Typically, the thickness of the thin conductive protons film is 300 μm or less.

The polymeric material is not specifically limited to any kind, provided that it is to the extent possible, prevents proton conductivity (due to reaction with the fullerene derivative or other) and has film-forming ability, and as a rule, it can be selected from polymers having electronic conductivity and exhibiting good stability. Examples of these polymers may include poliferation, polyvinylidene fluoride and polyvinyl alcohol. The reason poliferation, polyvinylidene fluoride and polyvinyl alcohol are suitable for the second proton conductor in this embodiment of the invention, will be described below.

The reason poliferation suitable for the second proton conductor, is it a good film-forming ability. Even when adding poliferation to fullerene derivative in a quantity less than the amount of the other polymer of the second material, you can easily get with a high resistance thin film of the second proton conductor. The content of poliferation is 3 wt.% or less, and preferably is in the range from 0.5 to 1.5 wt.%. When adding poliferation to fullerene derivative in a quantity within the above interval, a thin film of the second proton conductor has a thickness that can vary from 1 micron to 100 microns.

The reason polyvinylidene fluoride or polyvinyl alcohol are suitable for the second proton conductor, is that they effectively form a conductive protons thin film having a good ability to prevent the penetration of gases. The content of these materials in this case is preferably in the range from 5 to 15 wt.%.

If the content of the polyvinylidene fluoride or polyvinyl alcohol is less than the lower boundary of the above-mentioned interval, it can adversely affect the formation of the film.

A thin film of the second proton conductor in this embodiment of the invention can be obtained using any known method of forming films, such as extrusion, filtration, coating and other

The second proton conductor in this embodiment of the invention, prefer the LNA can be used for electrochemical devices uses a proton conductor according to the present variant embodiment of the invention.

Thus, in an electrochemical device that uses this version of the invention, in which the proton conductor is located between the first and second electrode, the proton conductor can be replaced by a second proton conductor in this embodiment of the invention.

Figure 10 shows a schematic representation of hydrogen-air element, which uses the second proton conductor as described with reference to Fig.9 variant embodiment of the invention. In this device the hydrogen electrode 21 is located opposite the air electrode 22, and between them is a proton conductor 20 in the form of a thin film (which given the configuration of the second proton conductor), and the outer side of the electrodes 21 and 22 are located between the Teflon plate 24A and a Teflon plate 24b having a number of holes 25, and is attached thereto by means of bolts 26a and 26b and nuts 27A and 27b, a rod 28a of the hydrogen electrode and the terminal 28b of the air electrode, which are continuations of the electrodes 21 and 22 protrude from the element.

Figure 11 shows schematically an Electromechanical device that uses a second proton conductor as described with reference to Fig.9 vari the NTU embodiment of the invention. Figure 11 shows that the proton conductor 34 (having the configuration of the second proton conductor) is located between the negative electrode 31 having on its inner surface layer 30 of the active material of the negative electrode and the positive electrode (gas electrode) 33 having on its outer surface of the substrate 32 to gas penetration. The active material of the negative electrode can be made in the form of absorbing hydrogen alloy or in the form of absorbing hydrogen alloy substrate of carbonaceous material, such as fullerene. The substrate 32 for penetration of gas can be made in the form of a porous carbon paper. Positive carbon 33 preferably made by coating a platinum paste to the substrate of the carbon powder. The gaps between the outer ends of the negative electrode 31 and the outer ends of the positive electrode 33 are closed by the gasket 35. In this electrochemical device charging can be done by ensuring the presence of water on the side of the positive electrode 33.

On Fig schematically depicts an Electromechanical device that uses a second proton conductor in this embodiment of the invention. On Fig shown that the proton conductor 41, made in the form of a thin film (which is attached to figurate second proton conductor), located between the negative electrode 38 having on its inner surface a layer 37 of the active material of the negative electrode and the positive electrode 40 having on its inner surface a layer 39 of the active material of positive electrode. The active material of positive electrode, usually made in the form of material, which is essentially the Nickel hydroxide. In this electrochemical device also gaps between the outer ends of the negative electrode 38 and the outer ends of the positive electrode 40 are closed by strips 42.

Each of the above-described electrochemical devices that use the second proton conductor in this embodiment of the invention can exhibit good proton conductivity, based on the same mechanism as in the electrochemical device, which uses a proton conductor in this embodiment of the invention. In addition, since the second proton conductor containing fullerene derivative in combination with a polymeric material, has a film-forming properties, it can be done in the form of a thin film of high strength and low permeability, and therefore it can be good proton conductivity.

A third option OS the implement of the present invention is described below. This third version is different from the first and second options the fact that the proton conductor is essentially composed of a derivative or derivatives of carbon clusters, but in other respects it is identical or similar to the first and second variants of the invention, for example, in such basic functions as the mechanism of proton conductivity.

The third proton conductor in this embodiment, the present invention essentially consists of derived carbon clusters, where the dissociation of protons entered in the number of atoms of each cluster or carbon clusters, which are used as starting material to obtain a derived carbon cluster.

Research conducted by the author of the present invention, showed that giving carbonaceous material satisfactory proton conductivity it is necessary to provide in the carbonaceous material as much as possible the number of paths of conduction of protons (sites or channels of conductivity). Found that satisfactory proton conductivity can be obtained in the form of the total value, if you are using carbon cluster, with a possible smaller size, and on its outer side put two or more dissociable protons deputies. In this case designed in the form of solids, the proton conductor greatly improves its properties in the acidic environment. However, unlike other carbon materials carbon cluster is not damaged by oxidation and more durable, and structure-forming carbon atoms of the cluster are strongly related to each other, resulting interatomic bond is not broken, i.e. less likely chemical changes, even in conditions of high acidity that allows you to save the film structure.

The third proton conductor in this embodiment of the invention having the above-described configuration can demonstrate, even in the dry state, high proton conductivity, similar to this index as the first and second proton conductors in the first and second embodiments of the invention.

As defined above, a cluster refers to a unit, composed of up to several hundreds of carbon atoms that are strongly related to each other. Thanks to this aggregated structure, the proton conductivity is improved, and at the same time, the chemical properties are preserved, which provides sufficient film strength and ease of formation of the layered structure. On the other hand, cluster, consisting mostly of carbon atoms, denotes the unit, which consists of up to several hundreds of atoms, which are closely connected together, regardless of the molecular type of connection that exists between separate the carbon atoms. It should be noted that the carbon cluster, i.e. the unit, which essentially consists of carbon atoms, not necessarily entirely made up of only carbon atoms. With this in mind, a set of atoms, most of which are carbon atoms, in the description of the present invention is called a carbon cluster. Different types of carbon clusters or aggregates of carbon atoms is shown in Fig. 4 through 7. In these figures the group dissociation of protons, for example hydroxyl groups, not shown. From these figures it is seen that the materials for proton conductors is very diverse, which allows you to have a wide choice.

Figure 4 shows the carbon clusters having a spherical structure, spheroid structure and similar planar structure. Figure 5 shows the carbon clusters with partially open spherical structure, which is characterized by an open end or ends. While obtaining fullerene molecules using arc discharge produces a great amount of carbon clusters having a spherical structure with open ends, as by-products. Figure 6 shows the carbon clusters, each of which has a diamond structure, in which most of the carbon atoms of the carbon cluster are SP3connection.

Material carbon cluster, to the or most of the carbon atoms are SP 2link if it has a planar structure of graphite or if it is fully or partially has the structure of a fullerene or nanotube, is undesirable as a source of material to obtain a proton conductor, because he often has an electronic conductivity due to SP2connection.

Conversely, fullerene structure or the structure of the nanotubes with SP2communication often has no electronic conductivity, as it also partially contains an element that demonstrates the desired SP3connection, and is therefore desirable as a starting material to obtain a proton conductor.

7 shows the carbon clusters, which are connected with each other. Thus, in the figure 7 presents examples of carbon clusters, which can be used to obtain derived carbon cluster for proton conductor in one of the embodiments of the third proton conductor of the present invention.

To get the third proton conductor in this embodiment of the invention, it is necessary to introduce the group to the dissociation of protons in clusters or in carbon clusters. In addition, it may be desirable to introduce also attracts electrons group in each cluster or carbon cluster. Group dissociation FR is new, you can enter in each carbon cluster using the following retrieval method.

In accordance with the method of obtaining of the present invention derived carbon cluster can be easily obtained by obtaining carbon clusters in the form of carbon powder using arc discharge carbon-based electrode, with subsequent appropriate acid treatment of carbon clusters, usually with the use of sulfuric acid, and hydrolysis, as well as through the application of sulfonation or phosphating, to introduce functional groups, respectively based on the sulfur or phosphorus.

Derived carbon cluster can be sealed, giving it a suitable form, such as tablet form. The third variant of the proton conductor of the present invention is characterized by the fact that the length of the major axis of each of the carbon clusters as source material for obtaining derivatives of carbon clusters for proton conductors, may be 100 nm or less, preferably 100 angstroms or less, and the number put into them functional groups may preferably be 2 or greater.

Carbon cluster used for the third variant of the proton conductor of the present invention may have a structure of at least part of which has open ends. Carbon cluster having such defective structures is, has reactivity similar to the reactivity of the fullerene, and in addition, has a higher reactivity for their defective parts, i.e. parts or parts with open ends. Accordingly, the use of carbon clusters, each of which has such a defective structure, i.e. the open end or ends, as the source material for the production of the third proton conductor may facilitate the introduction of substituents, dissociable protons, using acid or the like, processing, and thus to increase the efficiency of introduction of substituents, dissociable protons, and thus increase the proton conductivity of the third proton conductor. In addition, it is possible to synthesize a greater amount of carbon clusters compared to fullerene molecules, and consequently, to obtain carbon clusters at very low cost.

The kinds of functional groups and attracts electrons groups to be the introduction to each of the carbon clusters as source material for obtaining a third variant of the proton conductor of the present invention, can be the same as described above.

The third option is the implementation of a proton conductor according to the present invention suitable for use in various types of electrochemical devices such as fuel cells. In this case, the configuration is of the electrochemical device may be basically the same as for electrochemical device that uses the first or second proton conductors in the first or second embodiments of the invention, except that the first or second proton conductor is replaced by the third proton conductor. Since the third proton conductor in this embodiment of the invention also can exhibit good proton conductivity even in a dry condition, it is possible to eliminate the need to use a humidifier or other similar devices, which creates the environment for external migration, such as water or steam, and therefore, to simplify the system configuration and to reduce the mass of the system.

The following describes the fourth variant embodiment of the invention, in which the proton conductor includes a derived tubular carbonaceous material.

Derived tubular carbonaceous material includes a tubular carbonaceous material as a starting material to obtain it. The tubular carbonaceous material includes CNT-material (carbon nanotubes), consisting of molecules of nanotubes, each of which has a diameter of about several nanometers or less, typically in the range from 1 to 2 nanometers. In addition to the CNT material, the tubular carbonaceous material includes CNF-material (carbon nanofibers), consisting of m is of the molecules of nanofibers, each of which has a diameter of about several nanometers or more, and their length can reach up to 1 mm. In addition, it is known that CNT-material includes a material consisting of single-walled carbon nanotubes (SWCNT-material consisting of molecules of nanotubes, each of which is formed as a single layer, and a material consisting of multiwalled carbon nanotubes (MWCNT material)consisting of molecules of nanotubes, each of which is formed in the form of two or more layers, which cover concentrically to each other. The configuration of the molecules SWCNT and MWCNT, respectively, as shown in figa and 13B. In addition, note that the description of CNT materials, SWCNT and MWCNT is only illustrative, and the scope of the present invention is not restricted by them in their application.

In accordance with the fourth embodiment of the present invention, groups of dissociation of protons, which is introduced into the tubular carbonaceous materials in order to find the derivatives of the tubular carbonaceous material include the same groups dissociation of protons, which are described previously in relation to other embodiments of the present invention. As an illustration, figure 14 shows an example of a derived tubular carbonaceous material containing hydroxyl functional groups. Also, on Fig shows the number of tubular carbon molecules or tubular molecules derived tubular carbonaceous material, shown in Fig. On Fig also depicted tubular molecules, but of a different derivative of the tubular carbonaceous material, which includes a functional group-OSO3N.

Such derived tubular carbonaceous material obtained by the manufacturing halogenated tubular carbonaceous material and processing it halogenated material acid using sulfuric or nitric acid, to introduce a functional group-OSO3H in a tubular carbonaceous material, in order to obtain its derivative. In addition, there may be used a method of hydrolysis to introduce a hydroxyl group instead of functional groups-OSO3N. If using hydrolysis, then it can be used acid treatment to replace hydroxyl groups with other functional groups, such as functional group-OSO3N. If the source or raw material for obtaining the derivatives of the tubular carbonaceous material used dehalogenation tubular carbonaceous material, this material may be subjected to acid treatment using sulfuric or nitric acid, as described is use. As halogenated tubular carbonaceous material is preferable to use fluorine.

Derived tubular carbonaceous material can be obtained not only the above-described wet method, but also following a dry process that uses plasma. In this way dehalogenation tubular carbonaceous material is subjected to plasma treatment in oxygen, and then subjected to further plasma treatment in a nitrogen atmosphere to enter into the tubular molecules of the tubular carbonaceous material to the dissociation of protons, typically hydroxyl group.

The preceding description is non-limiting the present invention the explanation of the preferred method of manufacturing a tubular carbon material, which the present invention is not limited to.

The inventor investigated the proton conductivity of the derivatives of these tubular carbon materials and found that these materials provide high proton conductivity in a wide temperature range, including the range of temperatures common environment, i.e. the temperature below the freezing point of water and to a temperature above the boiling point of water (at least from -40°160°). The author of the present invention also found that the proton conductivity in the above those derived tubular carbonaceous material, which include hydrosulphate groups instead of hydroxyl groups.

In particular, polyhydroxyalkane SWCNT material is the generic name is derived, has a structure in which many hydroxyl groups added to the row of tubular molecules with the formation of SWCNT material shown on Fig. Of course, there may be some variations in the number, location and similar characteristics of hydroxyl groups, is not beyond the scope of the present invention. The present invention first determines that the unit polyhydroxyalkane tubular molecules, namely polyhydroxyalkane SWCNT material, such as shown in Fig and 15, in which the hydroxyl group of the tubular molecules are located next to each other, interact with each other, shows high proton conductivity, i.e. high ability to move or migration of ions N+or of hydrogen protons of the phenolic hydroxyl groups contained in each of the tubular molecules polyhydroxyalkane SWCNT material or solid material.

The purpose of the present invention can also be achieved by using a proton conductor, consisting mainly of a mass of units derived carbon tubular material having many groups-OSO3N, such as the masses of the SWCNT aggregates, with many groups-OSO3H. on the other hand, hydrosulphate ester SWCNT, in which group HE substituted groups OSO3N, may contain only groups OSO3N, as shown in Fig, or can contain many hydroxyl groups and many groups OSO3N in the same molecule.

Proton conductivity derived carbon tubular material comprising a tubular aggregates of molecules with several functional groups as proton conductivity other embodiments proton conductors, not limited by environmental conditions. This is because an additional source of protons from migration environments, such as water, is not required to obtain the desired effects of the present invention.

As in other embodiments, implementation of the present invention, the reason that derived carbon tubular material can exhibit the desired effect of proton conductivity in this case is that a large number of functional groups that can be introduced in a number of tubular molecules of the tubular carbonaceous material, so that the proton density, which corresponds to the conductivity per unit volume of the conductor is very high.

In addition, the derived tubular angle is odiogo material consists mainly of carbon atoms of each of the tubular molecules, and so it has a small weight and does not decay, because it contains almost no impurities. In addition, the tubular carbonaceous material, which is used as starting material to obtain the derivative, can be low cost to obtain by catalytic thermal decomposition of hydrocarbons. As a result, the tubular carbonaceous material is regarded as the preferred material from the viewpoint of saving resources, as well as from the point of view of operation in environmental conditions (Carbon Vol.36, No.11, 1998, s-1612).

According to the author the present invention by the research groups of the dissociation of protons used in the invention group dissociation of protons are not limited to functional hydroxyl or-OSO3N-groups, which are only preferred options groups, providing proton conductivity.

More specifically, the group dissociation of protons can be expressed by a chemical formula XH, where X represents any atom or atomic group having a bivalent connection, and in addition, this group can be expressed by a chemical formula HE or YOH, where Y is any atom or atomic group having a bivalent connection.

In particular, the group dissociation of protons preferably represent FDS is th at least one of the functional groups-HE-OSO 3H and-COOH, -SO3N-ORO(OH)3.

In addition, the group dissociation of protons entered into these derivative are the same as in the above examples.

In accordance with this embodiment of the present invention group, attracts electrons, such as nitro, carbonyl groups and carboxyl groups, nitrile groups, alkylhalogenide groups or halogen atoms (fluorine atoms or chlorine), preferably can be entered, together with the dissociation of protons in the atoms of carbon tubular carbonaceous material. For example, the group attracts electrons: -NO2, -CN, -F, -CL, -COOR, -Cho, -COR, -CF3or-SO3CF3(R represents an alkyl group) can be entered in the SWCNT, as well as group dissociation of protons, such as group IT. If there are groups that attracts electrons, in addition to the functional groups, protons, it can easily be removed from groups dissociation of protons and transferred between groups dissociation of protons through the attraction effect of electron groups, attracts electrons.

With regard to the number of groups to the dissociation of protons derived tubular carbonaceous material, this amount is limited to the value, which is smaller than the number of carbon atoms derived tubular carbon is the material. In addition, the number of functional groups may be limited to the amount necessary to eliminate electronic conductivity. For example, this number is preferably one or more groups to 10 carbon atoms for SWCNT material.

The proton conductor of the present invention is composed mainly of the above-mentioned tubular carbonaceous material and may also contain other components, which do not reduce or increase the proton conductivity. Most preferred among these other components is a derivative of fullerene, which has included the above-mentioned groups dissociation of protons.

Among the advantages of carbon tubular material, a significant length of the axial direction of the tube, which is greater than its axial length, and the intricate interweaving of the respective structures described above. Because of these advantages, you can get more durable and more resistant films when applying this material in electrochemical devices than in the case when aggregate with each other fullerene derivative in the form of spherical molecules. However, since the reaction of introducing groups to the dissociation of protons in the case of fullerene can occur more easily and it is possible to obtain a high conductivity, it is preferable to use these two mA is eriala to choose from, depending on the particular application.

If obtaining a composite material consisting of two different materials, use a combination of carbon tubular material, which introduced the group to the dissociation of protons, and derivatives of fullerene, which introduced the group to the dissociation of protons, it is possible to further improve performance.

In accordance with the present invention derivatives of the tubular carbonaceous material can be molded in the form of a film intended for use in an electrochemical device, such as a fuel element.

These materials can be molded in the form of a film by using a known extrusion method, and more preferably by dispersion derived tubular carbonaceous material in a liquid and filtering the resulting dispersion. As fluid is usually used solvent, such as water. However, the liquid used specifically in this example is not limited, provided that this derivative may be dispersed in the liquid.

Derived tubular carbonaceous material was obtained in the form of deposits on the filter film by filtering the dispersion. This film contains no binder and consists only of derived tubular carbonaceous material to the torus tubular molecules are intertwined in complex ways. This film has a very high strength and can be easily removed from the filter.

When the fullerene derivative dispersed in a liquid, in combination with the derived tubular carbonaceous material, you can easily obtain a composite film consisting of a combination of these materials, which also contains no binder.

The proton conductor according to this variant embodiment of the invention is preferably used for a fuel cell. As for the previous variant of the invention, the structure of a fuel cell such as shown in Fig.9.

The characteristics and advantages of the present invention will become clear from the following detailed description of a particular non-limiting variants of its implementation.

Synthesis polyhydroxyalkane fullerene of example 1.

Synthesis polyhydroxyalkane fullerene was carried out according to the method known from the publication L.Y. Chaing, L.Y. Wang, J.W. Swirczewski, S. Soled and S. Cameron, J. Organ Chem., (1994), 59, 3960. First, 2 g of a powder mixture of Co60and Co70containing about 15% Co70, was placed in 30 ml of fuming sulfuric acid and was stirred for three days in a nitrogen atmosphere at 60°C. the Reaction mixture in small portions was introduced in anhydrous diethylether, cooled in an ice bath, the precipitate was fractionally by centrifuge RA the division, twice washed with diethyl ether and twice with a mixture of diethyl ether and acetonitrile in the ratio of 2:1, and then dried under reduced pressure at a temperature of 40°C. Cleaned and dried thus precipitate was placed in 60 ml of ion exchange water and stirred for 10 hours at 85°With, at the same time exposing its bubbling with nitrogen. The reaction mixture was subjected to centrifugal separation to isolate the precipitate, which is then repeatedly washed with pure water, again subjected to centrifugal separation and dried under reduced pressure at a temperature of 40°C. thus Obtained brown powder was subjected to measurement by the method of FT-IR (infrared spectroscopy with Fourier transform). The measurement results showed that the infrared spectrum of this brown powder is almost completely corresponded to the range of C60(OH)12presented in the above document, and therefore, it was confirmed that the powder is polyhydroxylated fullerene, i.e. the target product. The above reaction is, for example, for C60as follows:

Obtaining tablets of units polyhydroxyalkane fullerene of example 1.

Next 90 mg powder polyhydroxyalkane fullerene extruded in one the direction under pressure of about 5 tons/cm 2, giving it shape round tablets with a diameter of 15 mm As the compaction of the powder polyhydroxyalkane fullerene was excellent despite the fact that this powder does not contain any binder resin, the powder polyhydroxyalkane fullerene can be easily molded into a tablet with a thickness of about 300 μm. This tablet hereinafter called the tablet of example 1.

Synthesis hydrosulfate-esterified of polishlanguage (full esterification) example 2

Synthesis hydrosulfurous fullerene was carried out as described in the above document. First, 1 g of powder polyhydroxyalkane fullerene were placed in 60 ml of fuming sulfuric acid and was stirred for three days in a nitrogen atmosphere at ordinary temperature. The reaction mixture in small portions was introduced in anhydrous diethylether, cooled in an ice bath, the precipitate was fractionally by centrifugal separation, washed three times with diethyl ether and twice with a mixture of diethyl ether and acetonitrile in the ratio of 2:1, and then dried under reduced pressure at a temperature of 40°C. thus Obtained powder was subjected to measurement by the method of FT-IR (infrared spectroscopy with Fourier transform). The measurement results showed that the infrared spectrum of this powder is almost fully meet the al spectrum hydrosulfurous fullerene, in which hydroxyl groups have been completely replaced hydrosulphate groups, i.e. groups-OSO3N, shown in the above document, and therefore, it was confirmed that the powder is hydrosulfurous fullerene, i.e. the target product.

The above reaction is, for example, for C60(OH)ylooks like this (here and below):

Getting pills from aggregates the hydrosulfate - esterified of polishlanguage example 2

Then 70 mg of powder hydrosulfurous fullerene extruded in one direction under the pressure of about 5 tons/cm2, giving it shape round tablets with a diameter of 15 mm As the compaction of the powder hydrosulfurous fullerene was excellent despite the fact that this powder does not contain any binder resin, the powder hydrosulfurous fullerene can be easily molded into a tablet with a thickness of about 300 μm. This tablet hereinafter called the tablet of example 2.

Synthesis of partially hydrosulfate-esterified of polishlanguage (partial esterification)

First, 2 g of a powder mixture of Co60and Co70containing about 15% Co70, was placed in 30 ml of fuming sulfuric acid and was stirred for three days in a nitrogen atmosphere at 60°C. the Reaction is mesh small portions were injected into diethylether, chilled in an ice bath. It should be noted that used diethylether not subjected to dehydration. Thus obtained precipitate was fractionally by centrifugal separation, washed three times with diethyl ether and twice with a mixture of diethyl ether and acetonitrile in the ratio of 2:1, and then dried under reduced pressure at a temperature of 40°C. thus Obtained powder was subjected to measurement by the method of FT-IR (infrared spectroscopy with Fourier transform). The measurement results showed that the infrared spectrum of this powder is almost completely corresponded to the spectrum of the fullerene derivative containing hydroxyl groups and group-OSO3N described in the above document, and therefore, it was confirmed that the powder is polyhydroxy-hydrosulfurous fullerene, i.e. the target product. The above reaction is, for example, for C60as follows (here and below):

Getting pills from aggregates the hydrosulfate-esterified of polishlanguage example 3

Next, 80 mg of powder polyhydroxy-hydrosulfurous fullerene extruded in one direction under the pressure of about 5 tons/cm2giving it the shape of round tablets with a diameter of 15 mm As the compaction of the powder is CA polyhydroxy-hydro-sulfated fullerene was great despite the fact that this powder does not contain any binder resin, the powder polyhydroxy-hydrosulfurous fullerene can be easily molded into a tablet with a thickness of about 300 μm. This tablet hereinafter called the tablet of example 3.

Obtaining tablets of fullerene aggregates of comparative example 1

For comparison, 90 mg of powder consisting of fullerene molecules, used as raw material for synthesis in the examples above, extruded in one direction under the pressure of about 5 tons/cm2giving it the shape of round tablets with a diameter of 16 mm Because the compaction of a powder consisting of fullerene molecules, was relatively high, despite the fact that this powder does not contain any binder resin, the powder consisting of fullerene molecules, could be relatively easily molded into a tablet with a thickness of about 300 μm. This tablet hereinafter called the tablet of comparative example 1.

Measurement of the proton conductivity of the tablets of examples 1 to 3 and comparative example 1

To measure the proton conductivity of each of the tablets of examples 1 to 3 and comparative example 1, the sides of the tablet was placed between aluminum plates are the same diameter as the tablet, ie 15 mm, and the tablet was applied AC voltage (range: 0,1 V), often with the Oh from 7 MHz to 0.01 Hz, to measure the impedance in the complex form at each frequency value. The measurements were carried out in a dry atmosphere.

As for the above measurement of the impedance, conducting protons part 1 proton conductor composed of the above tablets in electrical relation is an equivalent circuit shown in figa, in which the capacitance of 6 and 6' formed between the first and second electrodes 2 and 3, the conductive protons part 1, which is expressed by a parallel circuit of the resistance 4, and the capacitive resistance 5 located between them. In addition, capacitance 5 indicates the effect of delay (lag phase at high frequency) due to the migration of protons, and the resistance 4 denotes a parameter difficulties proton migration.

The measured impedance Z is expressed by the equation Z=Re(Z)+i·Im (Z). Using measurements studied the dependence of conductivity on frequency for conducting protons part, expressed the above equivalent circuit.

In addition, Fig In shows an equivalent circuit of the proton conductor (the above-described comparative example 1), in which he used the typical fullerene molecule without functional groups.

On Fig shows the results of measuring the total resistance of the tablets when the EPA 1 and comparative example 1.

As can be seen from Fig, for comparative example 1, the frequency characteristics of impedance in complex form is almost the same as for a single capacitor, and the conductivity of the charged particles (electrons, ions, etc.) Assembly of fullerene molecules is not observed at all. At the same time, for example 1 of the present invention the impedance at high frequencies has the appearance of a flattened, very smooth semicircular arc, showing the conductivity of some of the charged particles in the tablet, and expressed the imaginary number part of the impedance in the low frequency range has grown rapidly, which indicates the presence of blocking charged particles between the aluminum electrode and a tablet, as a gradual approach to the DC voltage. As for the blocking of charged particles between the aluminum electrode and the tablet in example 1, the charged particles on the side of the aluminum electrode are electrons, and thus it is clear that the charged particles in the tablets are not electrons or "holes", and are ions, and more specifically, protons, given the configuration of the fullerene derivative.

The conductivity of the above-described charged particle can be calculated by the intersection of the circular arc on the high side of the frequency axis X. For the tablets of example 1 conductivity for agennix particles is about 5· 10-6Cm/see Tablets of examples 2 and 3 according to the present invention were subjected to the same measurements as described above. In the full form in each of the frequency characteristic of impedance of each of examples 2 and 3 was similar to that observed in example 1; however, as can be seen from table 1, the conductivity of the charged particles of each of examples 2 and 3, calculated on the basis of the interception rounded-arc part of the X-axis, differed from those obtained in example 1.

Table 1.

Conductivity tablets proton conductors in examples 1, 2 and 3 according to the present invention (at 25°)
View tabletsConductivity (s/Cm)
Example 15×10-6
Example 29×10-4
Example 32×10-5

As shown in table 1, the conductivity tablets derivative of fullerene-containing group,- OSO3N, causes the ionization of hydrogen is lighter in comparison with containing hydroxyl groups. The results presented in table 1 also indicate that the unit fullerene derivative containing a hydroxyl group and group OSO3N, may be in a dry atmosphere good proton conductivity of the ri ordinary temperature.

Full impedance of the tablets obtained in example 1 was measured in the temperature range from -40°160°C. Expected conductivity tablets based on the rounded-arc portion on the side of the high frequency curve complex impedance of this tablet, measured at each temperature in order to study the dependence of conductivity on temperature. From the results presented on Fig (graph Arrhenius equation), it is seen that the conductivity is linearly varied with temperature variation within the measured temperature range -40°160°C. in Other words, the data Fig show that the conductivity mechanism of individual ions may act at least in the temperature range from -40°160°C. Therefore, the proton conductor, essentially consisting of producing fullerene according to the present invention can exhibit good proton conductivity in a wide temperature range from -40°to 120°including temperature normal environmental conditions.

Education film, including polyhydroxyalkane fullerene of example 1, and the experiment generation with this film

Powder polyhydroxyalkane fullerene (0.5 g) of example 1 of the examples 1 to 3 was mixed with 1 g of tetrahydrofuran (THF) and the resulting mixture was subjected to ultrasound is howling vibration for 10 minutes, that led to the complete dissolution polyhydroxyalkane fullerene in THF. After fabrication of the carbon electrode was obtained a film of polyhydroxyalkanoic fullerene, during the following steps: coating the surface of the electrode plastic mask with a rectangular hole; burying the above solution in this hole; a uniform distribution of the solution in the hole; drying at room temperature for evaporation of THF; and removing the mask. The same number of the above electrode was placed on the film, down to the surface, on which were the catalyst. The upper electrode was pressed under a pressure of about 5 tons/cm2to obtain the composite. This composite included in the fuel cell, as shown in Fig.9. An experiment on the production of electricity was carried out by feeding nitrogen gas to one electrode and air - to another electrode in the fuel element.

The result of the experiment shown in Fig 20. Voltage open circuit was about 1.2 V, and voltage values of the closed loop were also excellent; the voltage values shown on the graph against the values of current for a given fuel element.

Obtaining tablets 4A of polyhydroxyalkanoic fullerene of example 4.

First, 70 mg of the powder of the fullerene derivative obtained by wiseup the sliding synthesis, was mixed with 10 mg of powder of polyvinylidene fluoride, and then to the mixture was added 0.5 ml of dimethylformamide, and mixed powders were mixed in the solvent. The mixture was poured into a circular mold having a diameter of 15 mm, and the solvent evaporated under reduced pressure. Then the mixture from which boiled away the solvent, extruded to obtain pellets with a diameter of 15 mm and a thickness of about 300 μm. This tablet was then called tablet 4A of example 4.

Obtaining tablets 4B of polyhydroxyalkanoic fullerene of example 4

Similarly, 70 mg of the powder of the fullerene derivative was mixed with a dispersion containing 60% of fine powder of polytetrafluoroethylene (PTFE)to the PTFE content was 1 wt.% of the total number. Produced batch. Involved so the mixture was molded into a tablet with a diameter of 15 mm and a thickness of about 300 μm. This tablet was then called tablet 4B of example 4.

Synthesis hydrosulfate-esterization of polishlanguage (full esterification) of example 5

Synthesis hydrosulfurous fullerene was carried out as described in the above document. First, 1 g of powder polyhydroxyalkane fullerene were placed in 60 ml of fuming sulfuric acid and was stirred for three days in a nitrogen atmosphere at ordinary temperature. The reaction mixture in small portions have introduced the anhydrous diethylether, chilled in an ice bath, the precipitate was fractionally by centrifugal separation, washed three times with diethyl ether and twice with a mixture of diethyl ether and acetonitrile in the ratio of 2:1, and then dried under reduced pressure at a temperature of 40°C. thus Obtained powder was subjected to measurement by the method of FT-IR (infrared spectroscopy with Fourier transform). The measurement results showed that the infrared spectrum of this powder is almost completely corresponded to the spectrum of the fullerene derivative in which hydroxyl groups have been completely replaced hydrosulphate groups specified in the present description, and therefore, it was confirmed that the powder was hydrosulfurous fullerene, i.e. the desired product.

Obtaining tablets 5A of the hydrosulfate-esterified of polishlanguage (full esterification) of example 5

First 70 mg powder hydrosulfurous fullerene derivative was mixed with 10 mg of powder of polyvinylidene fluoride, and then to the mixture was added 0.5 ml of dimethylformamide and mixed powders were mixed in the solvent. The mixture was poured into a circular mold having a diameter of 15 mm, and the solvent evaporated under reduced pressure. Then the mixture from which boiled away the solvent, extruded with obtaining tablets with diametral mm and a thickness of about 300 μm. This tablet was then called tablet 5A of example 5.

Getting a tablet 5V from the hydrosulfate-esterified of polishlanguage (full esterification) of example 5

Similarly, 70 mg of powder hydrosulfurous fullerene was mixed with a dispersion containing 60% of fine powder of polytetrafluoroethylene (PTFE), so that the PTFE content was 1 wt.% of the total, and made a batch. Involved so the mixture was molded into a tablet with a diameter of 15 mm and a thickness of about 300 μm. This tablet was then called tablet 5V example 5.

Synthesis hydrosulfate-esterified of polishlanguage (partial esterification) of example 6

First, 2 g of a powder mixture of Co60and Co70containing about 15% Co70, was placed in 30 ml of fuming sulfuric acid and was stirred for three days in a nitrogen atmosphere at 60°C. the Reaction mixture in small portions was introduced in diethylether, cooled in an ice bath. It should be noted that used diethylether not subjected to dehydration. Thus obtained precipitate was fractionally by centrifugal separation, washed three times with diethyl ether and twice with a mixture of diethyl ether and acetonitrile in the ratio of 2:1, and then dried under reduced pressure at a temperature of 40°C. thus Obtained powder p which has Dorgali measurement method using FT-IR (infrared spectroscopy with Fourier transform). The measurement results showed that the infrared spectrum of this powder is almost completely corresponded to the spectrum of the fullerene derivative containing hydroxyl groups and group-OSO3N, as described in the present invention, and therefore, it was confirmed that the powder is polyhydroxy-hydrosulfurous fullerene, i.e. the desired product.

Getting a tablet 6A of the hydrosulfate-esterified of polishlanguage (partial esterification) of example 6

First 70 mg powder polyhydroxy-hydrosulfurous fullerene derivative was mixed with 10 mg of powder of polyvinylidene fluoride, and then to the mixture was added 0.5 ml of dimethylformamide, and mixed powders were mixed in the solvent. The mixture was poured into a circular mold having a diameter of 15 mm, and the solvent evaporated under reduced pressure. Then the mixture from which boiled away the solvent, extruded to obtain pellets with a diameter of 15 mm and a thickness of about 300 μm. This tablet was then called tablet 6A of example 6.

Obtaining tablets 6B of the hydrosulfate-esterified of polishlanguage (partial esterification) of example 6

Similarly, 70 mg of powder polyhydroxyalkane hydrosulfurous fullerene was mixed with a dispersion containing 60% finely ground powder policyref is acetylene (PTFE), so that the PTFE content was 1 wt.% of the total, and made a batch. Involved so the mixture was molded into a tablet with a diameter of 15 mm and a thickness of about 300 μm. This tablet was then called tablet 6B of example 6.

Obtaining tablets fullerene comparative example 2

For comparison, 90 mg of powder consisting of fullerene molecules, used as raw material for synthesis in the above examples, were mixed with 10 mg of powder of polyvinylidene fluoride, and then to the mixture was added 0.5 ml of dimethylformamide and mixed powders were mixed in the solvent. The mixture was poured into a circular mold having a diameter of 15 mm, and the solvent evaporated under reduced pressure. Then the mixture from which boiled away the solvent, extruded to obtain pellets with a diameter of 15 mm and a thickness of about 300 μm. This tablet hereinafter called the tablet of comparative example 2.

Getting pills from fullerene comparative example 3

For comparison, 70 mg of powder consisting of fullerene molecules, used as raw material for synthesis in the above examples was mixed with a dispersion containing 60% of fine powder of polytetrafluoroethylene (PTFE), so that the PTFE content was 1 wt.% of the total, and made a batch. Involved thus see the camping was molded into a tablet with a diameter of 15 mm and a thickness of about 300 μm. This tablet hereinafter called the tablet of comparative example 3.

Measurement of the proton conductivity of the tablets of examples 4 to 6 and comparative example 2

To measure the proton conductivity of each of the tablets of examples 4 to 6 and comparative example 2, the sides of the tablet was placed between aluminum plates are the same diameter as the tablet, ie 15 mm, and the tablet was applied AC voltage with an amplitude of 0.1 V and a frequency of 7 MHz to 0.01 Hz to measure the impedance in the complex form at each frequency. The measurements were carried out in a dry atmosphere.

In these measurements the impedance conductive protons part 1 proton conductor composed of the above pill is electrically represented by an equivalent circuit shown in figa, in which the capacitance of 6 and 6' formed between the first and second electrodes 2 and 3, the conductive protons part 1, which is expressed by a parallel circuit of the resistance 4, and the capacitive resistance 5 located between them. In addition, capacitance 5 indicates the effect of delay (lag phase at high frequency) due to the migration of protons, and the resistance 4 denotes a parameter difficulties proton migration. The measured impedance Z is expressed by the equation Z=Re (Z)+i·Im (Z). The results of the measurements studied the dependence of conductivity on frequency for conducting protons part, expressed the above equivalent circuit. Figv represents the equivalent electrical circuit of the proton conductor (described below comparative example), which used a typical fullerene molecules without dissociation of protons.

On Fig depicts a graph showing the results of measuring the total resistance of the tablets 1A of example 4 and 4 tablets of comparative example 2.

As can be seen from Fig for tablets of comparative example 2, the frequency characteristics of impedance in complex form is almost the same as for a single capacitor, and the conductivity of the charged particles (electrons, ions, etc.) Assembly of fullerene molecules was not observed at all. At the same time for the tablets of example 4 of the present invention the impedance at high frequencies has the appearance of flattened, but very smooth semicircular arc, showing the conductivity of some of the charged particles in the tablet, and expressed the imaginary number part of the impedance in the low frequency range has grown rapidly, which indicates the presence of blocking charged particles between the aluminum electrode and a tablet, as a gradual approach to the DC voltage. As for the lock and the charged particles between the aluminum electrode and the tablet 1A of example 4, it should be noted that the charged particles on the side of the aluminum electrode are electrons, and therefore, the charged particles in the tablets are not electrons or "holes", and are ions, and more specifically in the proton, given the configuration of the fullerene derivative.

The conductivity of the above-described charged particle can be calculated based on the intersection of the graph in the form of a circular arc in the high frequency axis X. For the tablets of example 4, the conductivity of the charged particles is about 1×10-6Cm/see Tablets 1B of example 4 tablets of example 5 and the tablets of example 6 of the present invention were subjected to the same measurements as described above. In the full form of frequency characteristics of impedance in each of these tablets was similar to that observed in example 4; however, as shown in table 2, the conductivity of the charged particles in each of the tablets, calculated from the intersection of the graph in the form of a circular arc with the X-axis, different from the results obtained in this tablet.

Table 2.

Conductivity tablets proton conductors

in the examples of the present invention (at 25°)
View tabletsConductivity (s/Cm)
Tabla is ka 4A of example 4 1×10-6
Tablet 5A of example 52×10-4
Tablet 6A of example 66×10-5
Tablet 4B of example 43×10-6
Tablet 5V example 57×10-4
Tablet 6B of example 63×10-6

As shown in table 2, in tablets of type a and b of examples 4, 5 and 6, the conductivity tablets derivative of fullerene-containing groups OSO3N, higher than tablets fullerene derivative containing hydroxyl groups. The reason for this is that the group OSO3N can more easily cause ionization of hydrogen than hydroxyl groups. The results presented in table 2 also indicate that the unit fullerene derivative containing a hydroxyl group and group OSO3N, may be in a dry atmosphere good proton conductivity at ordinary temperature.

Next, the full impedance tablets 4A of example 4 was measured in the temperature range from -40°160°and expected conductivity tablets, taking into account the part of the graph in the form of a circular arc in the high frequency curve complex impedance of this tablet, measured at each value of temperature to study zavisimosti conductivity on temperature. The results are presented on Fig in the form of a graph Arrhenius equation. From the results presented on Fig, it is clear that there is a linear relationship between conductivity and temperature, at least within the measured temperature range -40°160°C. in Other words, the data Fig show that the conductivity mechanism of individual ions may act at least in the temperature range from -40°160°C. Therefore, the second proton conductor, essentially consisting of a fullerene derivative and the polymer material of the present invention, can exhibit good proton conductivity in a wide range temperature, including temperature normal environmental conditions, in particular in the range from -40°160°C.

Derivatization of carbon cluster of example 7

Arc discharge was obtained by passing the current value of 200 And between the two electrodes consisting of carbon plates, in an argon atmosphere at a pressure of 0.05 MPa, the result was obtained 1 g of carbon powder. This carbon powder was mixed with 100 ml of 60% fuming sulfuric acid and kept for three days in a stream of nitrogen at 60°C. Heating was performed using a water bath. The reaction solution was dropwise introduced into 500 ml of pure water, and the solid was isolated from the water rest the RA by centrifugal separation. The solid is repeatedly washed with anhydrous diethyl ether and was dried for five hours under reduced pressure at a temperature of 40°C. the resulting powder was dissolved in 10 ml of tetrahydrofuran (THF). The insoluble component was removed by filtration and the solvent evaporated under reduced pressure. The result has been solid, 50 mg which is then extruded under pressure of 5 t/cm2, and received a round tablet with a diameter of 15 mm, This tablet hereinafter called the tablet of example 7.

Measurement of proton conductivity tablet derived from carbon cluster of example 7

Impedance AC tablets of example 7 was measured in dry air, as described above. In the result, it was confirmed that the total resistance resulting from ionic conductivity, appeared at frequencies in the region of 10 MHz or below. The conductivity of the tablets of example 7, is calculated based on the diameter of the circular arc of the curve full resistance was 3.0×10-4(Cm/cm).

Derivatization of carbon cluster of example 8

Arc discharge was obtained by passing the current value of 200 And between the two electrodes consisting of carbon plates, in an argon atmosphere at a pressure of 0.05 MPa, resulting in a received 1 g of carbon powder. This carbon is the powder was dissolved in toluene, the insoluble component was removed by filtration and the solvent evaporated under reduced pressure, the result is again received powder. The resulting powder was mixed with 100 ml of 60% fuming sulfuric acid and kept for three days in a stream of nitrogen at a temperature of 60°C. Heating was performed using a water bath. The reaction solution was dropwise introduced into 500 ml of pure water, and the solid was isolated from the aqueous solution using a centrifuge separation. The solid is repeatedly washed with anhydrous diethyl ether and was dried for five hours under reduced pressure at a temperature of 40°C. the Obtained solid substance in a quantity of 50 mg extruded under a pressure of 7 t/cm2, and received a round tablet of example 8.

Measurement of the proton conductivity of the tablets of example 8

Impedance AC tablets of example 8 was measured in dry air as described above. In the result, it was confirmed that the total resistance resulting from ionic conductivity, appeared at frequencies in the region of 10 MHz or below. The conductivity of the tablets of example 8, is calculated based on the diameter of the circular arc of the curve full resistance was 3.4×10-4(Cm/cm).

The main component of the carbon powder obtained by the arc discharge, the submission is a carbon clusters or molecules of carbon clusters, not having completed the structure, such as cell structure, but having a structure of at least part of which has a free connection. In addition, the molecules having a structure with good electronic conductivity, similar to the graphite structure, which in small quantities among molecules, carbon clusters, hinder the implementation of the ion processing in example 7 and immediately after the arc discharge in example 8. In the method of the impedance to alternating current, it was confirmed that these pills do not have electronic conductivity. On Fig shows TOF-MS spectrum of the [and] the carbon powder obtained by the arc discharge. As shown in Fig, a large part of the carbon powder has a mass number average of 5500 or less, i.e. carbon number, consisting of 500 or less. Since the distance of the link between carbon atoms in the carbon powder is less than 2 angstroms, the diameter of each of the carbon clusters of the powder is less than 100 nm.

The following are examples, in which the carbon material used tubular carbonaceous material.

Synthesis of 1 polyhydroxyalkane SWCNT material

Received purified SWCNT material, then burned it in for 10 hours at a temperature of 250°in the atmosphere gazoobrazovateli to get polyfluorinated SWCNT. Polyfluorinated SWCNT were placed in pure water and subjected to heating in a flask under reflux for three days at a temperature of 100°C, With vigorous stirring, to replace the fluorine atoms of hydroxyl groups, and thereby to obtain polyhydroxyalkane SWCNT material, which was called as the material of example 9.

Synthesis hydrosulfurous SWCNT

Polyhydroxyalkane SWCNT obtained as in example 9, was placed in fuming sulfuric acid and within three days was stirred at a temperature of 60°to replace the hydroxyl group by the group OSO3H, and thereby to obtain hydrosulfurous SWCNT material, which was called as the material of example 10.

Synthesis of 2 polyhydroxyalkane SWCNT

Received purified SWCNT material was then subjected to oxygen plasma treatment. Then the atmosphere in the chamber was replaced with hydrogen, after which the material was subjected to hydrogen plasma treatment to get polyhydroxyalkane SWCNT material, which is identified as the material of example 11.

Receiving samples of films

Each of the above three materials were dispersible in the water, and the dispersion was filtered by suction through a filter paper with a pore size of 0.2 μm, to precipitate settled on the filter paper in the form of a film. The amount of the var the var, to be filtered, selected in such a way as to obtain a film having a thickness of 100 microns.

The film deposited on filter paper, can be easily removed from it. Thus obtained film was then called the films of examples 9, 10 and 11. The material obtained by mixing the material of example 10 with hydrosulfurous derivative of fullerene mass ratio of 1:1, filtered as described above, to obtain the film, which is identified as the film of example 12. Next, SWCNT material, containing no substituents, filtered as described above, to obtain the film, which is identified as the film of comparative example 4.

Measurement of the proton conductivity of the film

To measure the proton conductivity of each of the films of examples 9 to 12 and comparative example 4, the film was placed between sheets of aluminum foil, cut in the form of discs with a diameter of 15 mm. These discs were placed between the electrodes and the film was applied AC voltage with amplitude of 0.1 V and a frequency of 7 MHz to 0.01 Hz to measure the impedance in the complex form at each frequency. The measurements were carried out in a dry atmosphere.

The results of these measurements for the film of comparative example 4 described below. The complete resistance of this film was recorded at low SOP is Otellini, i.e. it has not been changed in all the above frequency range, due to the fact that the electronic conductivity of the SWCNT material of comparative example 4 high. The result found that the film of comparative example 4 could not be used as an ionic conductor.

The measurement results for the films of examples 9-12 of the present invention are described below. Full end to end resistance of the film of example 10 presents the schedule for Fig. From Fig it is seen that the impedance at high frequencies is very smooth circular arc, showing the conductivity of some of the charged particles in the film, and expressed the imaginary number part of the impedance in the low frequency range has grown rapidly, which indicates the presence of blocking charged particles between the aluminum electrode and the film, as gradual approximation to the DC voltage. As for the blocking of charged particles between the aluminum electrode and the film of example 10, the charged particles on the side of the aluminum electrode are electrons, and accordingly it is clear that the charged particles in the film are not electrons or "holes", and are ions, and more specifically, protons, given the structure of tubular carbon derived, forming this film. As for the plait is OK examples 9, 11 and 12, the behavior of these films was similar to the behavior of the film of example 10, although among them there were differences in the sizes of the circular arc. Based on this established that the films of examples 9-12 of the present invention possess the desired functions as derived carbon tubular material of the proton conductor.

As for the above measurement of the impedance, conducting protons part 1 linkoeping proton conductor is an equivalent electrical circuit in which capacitance is created between the first and second electrodes, the resistance in the conducting protons parts in between, just as described for the previous embodiments of the invention, and as illustrated in figa. In addition, the capacitance indicates the effect of delay (lag phase at high frequency) due to the migration of protons, and the resistance indicates the parameter difficulties proton migration. The measured impedance Z is expressed by the equation Z=Re (Z)+i·Im (Z). Studied the dependence of conductivity on frequency for conducting protons parts.

The conductivity of the above-described charged particle can be calculated based on the intersection of the circular arc in the high frequency x-axis Conductivity of the film of example 10 is left about 2× 10-5Cm/see the conductivity of the films in other examples according to the present invention differ, as shown in table 3.

Table 3.

The conductivity of the films proton conductors according to the present invention (at 25°)
View filmsConductivity (s/Cm)
The film of example 92×10-7
The film of example 102×10-5
The film of example 117×10-8
The film of example 123×10-4

As can be seen from table 3, when instead of hydrosulphate of functional groups in the tubular carbonaceous material injected group OSO3N, the proton conductivity of the film tends to increase. The reason for this is that the group OSO3N can better cause ionization of hydrogen than hydroxyl groups. The results show that the unit derived tubular carbonaceous material containing hydroxyl groups and group OSO3N, may be in a dry atmosphere good proton conductivity at ordinary temperature.

1. Proton conductor, comprising the carbonaceous material, which essentially consists of carbon Klah is terov, with many groups dissociation of protons, thereby providing them dissociation education protons, which can be described by the formula HN, where H represents the hydrogen atom or the formula-IT or-YOH, where O represents an oxygen atom, a X, Y represent any atom or atomic group, which are bivalent bond, and the carbon cluster is a cluster of molecules or a related molecule, containing from a few hundred to a few thousand atoms of carbon.

2. The proton conductor according to claim 1, wherein the carbon cluster is a fullerene molecule.

3. The proton conductor according to claim 1, wherein the carbon cluster has a structure including a fullerene structure, at least part of which has a free connection.

4. The proton conductor according to claim 1, wherein the carbonaceous material includes related to each other carbon clusters.

5. The proton conductor according to claim 1, characterized in that the group dissociation of protons selected from the group consisting of-OH, -OSO3H, -COOH, -So3N-ORO(OH)3.

6. The proton conductor according to claim 1, characterized in that the carbonaceous material group entered the dissociation of protons and groups that attracts electrons.

7. The proton conductor according to claim 6, wherein the group : what affect the electrons, selected from the group consisting of nitro groups, carbonyl groups, carboxyl groups, nitrile groups, alkylhalogenide groups and halogen atoms.

8. The proton conductor according to claim 1, characterized in that it essentially consists of carbonaceous material, which introduced the group to the dissociation of protons.

9. The proton conductor according to claim 1, characterized in that it essentially consists of carbonaceous material, which introduced the group to the dissociation of protons, and a polymeric material.

10. The proton conductor according to claim 9, characterized in that the polymeric material has an electronic conductivity.

11. The proton conductor according to claim 9, characterized in that the polymeric material is at least one material selected from the group consisting of poliferation, polyvinylidene fluoride and polyvinyl alcohol.

12. The proton conductor according to claim 9, characterized in that it comprises a polymeric material in the amount of 50 wt.% or less.

13. The proton conductor according to claim 9, characterized in that the polymeric material includes polytetrafluoroethylene in an amount of 3 wt.% or less.

14. The proton conductor according to claim 9, characterized in that it is made in the form of a thin film with a thickness of 300 μm or less.

15. Proton conductor, comprising the carbonaceous material, which essentially consists of carbon clusters, have their many groups dissociation of protons, providing at their dissociation education protons, which can be described by the formula HN, where H represents the hydrogen atom or the formula-IT or-YOH, where O represents an oxygen atom, a X, Y represent any atom or atomic group, which are bivalent bond, and the carbon cluster is a tubular carbonaceous material.

16. Proton conductor, comprising the carbonaceous material, which essentially consists of carbon clusters with multiple groups to the dissociation of protons, thereby providing them dissociation education protons, which can be described by the formula HN, where H represents a hydrogen atom, or formula HE or is HE, where O represents an oxygen atom, a X, Y represent any atom or atomic group, which are bivalent bond, and the carbon cluster has a rhomboidal (diamond) structure.

17. Proton conductor, comprising the carbonaceous material, which essentially consists of carbon clusters with multiple groups to the dissociation of protons, thereby providing them dissociation education protons, which can be described by the formula HN, where H represents the hydrogen atom or the formula-IT or-YOH, where O represents an oxygen atom, a X, Y represent any ATO is or atomic group, which are bivalent bond, and the carbon cluster is a cluster of carbon atoms, and the length of its major axis is 100 nm or less.

18. The proton conductor according to 17, comprising the carbonaceous material, which essentially consists of carbon clusters, and the length of the major axis of the carbon cluster is 100 Å or less.

19. The way to obtain a proton conductor comprising the step of introducing groups to the dissociation of protons, thereby providing them dissociation education protons, which can be described by the formula HN, where H represents the hydrogen atom or the formula-IT or-YOH, where O represents an oxygen atom, a X, Y represent any atom or atomic group, which are bivalent connection, in the carbonaceous material, essentially consisting of carbon clusters, which are clusters of carbon atoms, the length of the main axis of which is 100 nm or less.

20. The way to obtain a proton conductor according to claim 19, characterized in that halogenosilanes or dehalogenation the carbonaceous material used as a raw material, and the carbon atoms contained in the carbon material, introducing the group to the dissociation of protons, exposing the raw material to hydrolysis, plasma treatment or acid treatment.

21. SPO is about the reception of the proton conductor according to claim 19, characterized in that the carbon cluster use the fullerene molecule.

22. The way to obtain a proton conductor according to claim 19, wherein the carbon cluster structure comprising fullerene structure, at least part of which has a free connection.

23. The way to obtain a proton conductor according to claim 19, characterized in that the use of carbon material, which is related to each other carbon clusters.

24. The way to obtain a proton conductor according to claim 19, wherein the use includes carbon clusters, carbon material which is produced by arc discharge using an electrode based on carbon, is subjected to the acid treatment to introduce groups to the dissociation of protons contained in the carbon clusters, carbon atoms.

25. The way to obtain a proton conductor according to claim 19, characterized in that it includes the step of introducing groups to the dissociation of protons in the carbonaceous material and the step of sealing the carbonaceous material, which introduced the group to the dissociation of protons, to impart the required form.

26. The way to obtain a proton conductor according A.25, characterized in that the step of sealing includes the step of forming, in essence, only the carbonaceous material, which introduced the group dissocial and protons to give it the form of a film or tablet.

27. The way to obtain a proton conductor according A.25, characterized in that the step of sealing includes the step of mixing the polymer material with the carbonaceous material, which introduced the group to the dissociation of protons, giving a mixture of the forms of film or tablet.

28. The way to obtain a proton conductor according to item 27, wherein the use of the polymer material constituting at least one of the materials selected from the group consisting of poliferation, polyvinylidene fluoride and polyvinyl alcohol.

29. The way to obtain a proton conductor according to item 27, wherein the proton conductor includes a polymeric material in an amount of 50 wt.% or less.

30. The way to obtain a proton conductor according to item 27, wherein the use of the polymer material constituting the polytetrafluoroethylene in an amount of 3 wt.% or less.

31. The way to obtain a proton conductor according to item 27, wherein the proton conductor is formed into a thin film with a thickness of 300 μm or less.

32. The way to obtain a proton conductor comprising the step of introducing groups to the dissociation of protons, thereby providing them dissociation education protons, which can be described by the formula HN, where H represents the hydrogen atom or the formula-IT or-YOH, where is a and the ohms of oxygen, a X, Y represent any atom or atomic group, which are bivalent connection, in the carbonaceous material, essentially consisting of carbon clusters, representing a tubular carbonaceous material.

33. The way to obtain a proton conductor according p, characterized in that the tubular carbonaceous material after introducing groups to the dissociation of protons is dispersed in the fluid and filter for the formation of a film.

34. The way to obtain a proton conductor comprising the step of introducing groups to the dissociation of protons, thereby providing them dissociation education protons, which can be described by the formula HN, where H represents the hydrogen atom or the formula-IT or-YOH, where O represents an oxygen atom, a X, Y represent any atom or atomic group, which are bivalent connection, in the carbonaceous material, essentially consisting of carbon clusters having rhomboid (diamond) structure.

35. Electrochemical device comprising a first electrode, a second electrode, and a proton conductor located between the first and second electrodes, and a proton conductor includes a carbon material, essentially consisting of carbon clusters with multiple groups to the dissociation of protons, thereby providing them dissociation education FR is new, which can be described by the formula HN, where H represents a hydrogen atom, or formula HE or YOH, where O represents an oxygen atom, a X, Y represent any atom or atomic group, which are bivalent relationship in that the carbon cluster is a cluster of molecules or a related molecule, containing from a few hundred to a few thousand atoms of carbon.

36. Electrochemical device according to p, wherein the proton conductor has an ionic conductivity greater than its electronic conductivity.

37. Electrochemical device according to p, wherein the carbon cluster is a fullerene molecule.

38. Electrochemical device according to p, wherein the carbon cluster has a structure in which at least a part of fullerene structure has a loose connection.

39. Electrochemical device according to p, wherein the carbonaceous material includes related to each other carbon clusters.

40. Electrochemical device according to p, characterized in that the group dissociation of protons selected from the group consisting of-OH, -OSO3H, -COOH, -SO3N-ORO(OH)3.

41. Electrochemical device according to p, characterized in that the carbonaceous material group entered the dissociation of protons and gr is PPI, attracts electrons.

42. Electrochemical device according to paragraph 41, wherein the group attracts electrons selected from the group consisting of nitro groups, carbonyl groups, carboxyl groups, nitrile groups, alkylhalogenide groups and halogen atoms.

43. Electrochemical device according to p, wherein the proton conductor consists essentially of carbonaceous material, which introduced the group to the dissociation of protons.

44. Electrochemical device according to p, wherein the proton conductor comprises a carbon material, which introduced the group to the dissociation of protons, and a polymeric material.

45. Electrochemical device according to item 44, wherein the polymeric material has no electronic conductivity.

46. Electrochemical device according to item 44, wherein the polymeric material is at least one material selected from the group consisting of poliferation, polyvinylidene fluoride and polyvinyl alcohol.

47. Electrochemical device according to item 44, wherein the proton conductor comprises a polymeric material in an amount of 50 wt.% or less.

48. Electrochemical device according to item 44, wherein the polymeric material includes polytetrafluoroethylene in an amount of 3 wt.% or less.

49. Electrochemical device according to item 44, characterized in that it is made in the form of a thin film with a thickness of 300 μm or less.

50. Electrochemical device according to p, wherein the first electrode and/or the second electrode are gas electrodes.

51. Electrochemical device according to p, wherein the first electrode and/or the second electrode are electrodes comprising active materials.

52. Electrochemical device according to p, characterized in that it is made in the form of fuel element.

53. Electrochemical device according to p, characterized in that it is made in the form of hydrogen-air element.

54. Electrochemical device comprising a first electrode, a second electrode, and a proton conductor located between the first and second electrodes, and a proton conductor includes a carbon material, essentially consisting of carbon clusters with multiple groups to the dissociation of protons, thereby providing them dissociation education protons, which can be described by the formula HN, where H represents a hydrogen atom, or formula HE or YOH, where O represents an oxygen atom, a X, Y represent any atom or atomic group, which are bivalent linkage, with some carbon clusters to depict ablaut a tubular carbonaceous material.

55. Electrochemical device comprising a first electrode, a second electrode, and a proton conductor located between the first and second electrodes, and a proton conductor includes a carbon material, essentially consisting of carbon clusters with multiple groups to the dissociation of protons, thereby providing them dissociation education protons, which can be described by the formula HN, where H represents a hydrogen atom, or formula HE or YOH, where O represents an oxygen atom, and X, Y represent any atom or atomic group, which are bivalent linkage, with some carbon clusters have a diamond (diamond) structure.

56. Electrochemical device comprising a first electrode, a second electrode, and a proton conductor located between the first and second electrodes, and a proton conductor includes a carbon material, essentially consisting of carbon clusters with multiple groups to the dissociation of protons, thereby providing them dissociation education protons, which can be described by the formula HN, where H represents a hydrogen atom, or formula HE or YOH, where O represents an oxygen atom, and X, Y represent any atom or atomic group, which are bivalent relationship in that carbon is laster is a cluster of carbon atoms, the length of the main axis of which is 100 nm or less.

57. Electrochemical device according to p, characterized in that it includes a carbon material, essentially consisting of carbon clusters, and the length of the major axis of the carbon cluster is 100 Å or less.



 

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