Patent Grant
7749935
The present invention relates to a catalyst carrier. More particularly, the present invention relates to a catalyst carrier, which can be used as an electrode catalyst of a fuel cell, wherein a catalyst metal is carried on a carbon fiber; a production method for the catalyst carrier; and a fuel cell using the catalyst carrier.
A solid polymer type fuel cell is attracting attention to be used for a cell automobile and a portable power supply since it is compact and can obtain a high current density when operated at room temperature compared with a phosphoric-acid type fuel cell and a molten carbonate type fuel cell. Further, many proposals on components, system compositions and the like in such fields have been made. A stack structure of a conventional solid polymer type fuel cell is a sandwich structure of, for example, of separator/electrode (oxygen electrode)/electrolyte membrane/electrode (hydrogen electrode)/separator. Required characteristics of an electrode for this fuel cell are to prevent the electrode from poisoning by carbon monoxide and to enhance activity per unit amount of a catalyst metal. For the purpose of preventing such poisoning and enhancing the activity, many trials have been made to date on metals or alloys thereof to be used as catalysts as described in JP-A-2001-85020 (U.S. Pat. No. 6,689,505), which describes that a particle size of a catalyst is preferably several nm.
On the other hand, as for carbon to be used for a carrier, particulate carbon such as ordinary carbon black is used as described in JP-A-8-117598, JP-A-2003-201417 (EP 1309024) and JP-A-2001-357857. However, since the contact between carbon particles is conducted by a point contact, there is a problem that resistance is large and gas permeability is insufficient. In order to solve these problems, it has been considered effective to change the particulate carbon to fiber carbon to be used for the carrier as described in JP-A-7-262997, JP-A-2003-317742 and JP-A-2003-200052.
As for carbon fibers, a vapor-grown carbon fiber, a carbon nanotube and a PAN type carbon fiber are known. However, in any of reports which have been made public to date, a technique to produce an electrode comprising a carbon fiber on which fine catalyst particles are uniformly carried with a high density has not been described.
An object of the present invention is to provide a vapor-grown carbon fiber capable of enhancing an activity per unit amount of a catalyst metal, reducing a reaction resistance and enhancing an output density and appropriate as a catalyst carrier and the like, a catalyst carrier carrying a metal catalyst, production methods thereof and an application thereof for a fuel cell.
The present invention provides a catalyst carrier, a production method and an application thereof as follows:
1. A catalyst carrier, being characterized in that a catalyst metal for promoting an oxidation-reduction reaction is carried on a vapor-grown carbon fiber having an average outer diameter of from 2 nm to 500 nm, which has been subjected to a crushing treatment so as to have a BET specific surface area of from 4 m2/g to 100 m2/g and an aspect ratio of from 1 to 200.
2. The catalyst carrier as described in 1 above, wherein a ratio of an average fiber length after the crushing treatment to an average fiber length before the crushing treatment is 0.8 or less.
3. The catalyst carrier as described in 1 or 2 above, wherein a ratio of a specific surface area after the crushing treatment to a specific surface area before the crushing treatment is 1.1 or more.
4. The catalyst carrier as described in any of 1 to 3 above, wherein the vapor-grown carbon fiber is a carbon fiber comprising a branched vapor-grown carbon fiber;
5. The catalyst carrier as described in any of 1 to 4 above, wherein the catalyst metal is at least one metal selected from the group consisting of platinum and transition metals belonging to the groups IV and V in the periodic table or any one of alloys thereof.
6. A production method for a catalyst carrier, being characterized in that a catalyst metal for promoting an oxidation-reduction is supported on a vapor-grown carbon fiber having an average outer diameter of from 2 nm to 500 nm, which has been obtained by thermally decomposing hydrocarbon, or a vapor-grown carbon fiber obtained by performing a thermal treatment of the thus-obtained vapor-grown carbon fiber at a temperature of from 600° C. to 1300° C. in an atmosphere of an inert gas, which have been crushed so as to have a BET specific surface area of from 4 m2/g to 100 m2/g and an aspect ratio of from 1 to 200.
7. The production method for the catalyst carrier as described in 6 above, wherein support of the catalyst metal is performed by a liquid phase reduction method.
8. The production method for the catalyst carrier as described in 6 or 7 above, wherein, after being crushed, the vapor-grown carbon fiber is subjected to a thermal treatment at a temperature of from 2000° C. to 3000° C. in an atmosphere of an inert gas.
9. The production method for the catalyst carrier as described in 6 or 7 above, wherein, before being crushed, the vapor-grown carbon fiber is subjected to a thermal treatment at a temperature of from 2000° C. to 3000° C. in an atmosphere of an inert gas.
10. The production method for the catalyst carrier as described in any of 6 to 9 above, wherein such crushing is performed by dry crushing using an impact force.
11. The production method for the catalyst carrier as described in 10 above, wherein crushing is performed in an atmosphere containing oxygen in a concentration of 5% by volume or more.
12. A catalyst carrier obtained by the method as described in any of 6 to 11 above.
13. An electrode material, wherein a catalyst layer comprising a catalyst carrier as described in any of 1 to 5 and 12 above is formed on an electrically conductive base material.
14. A membrane electrode assembly for a fuel cell, which comprises an electrode wherein a catalyst layer and a gas diffusion layer are provided on both faces of an electrolyte membrane, being characterized in that the catalyst layer comprises the electrode material as described in 13 above.
15. A cell of a fuel cell, comprising the membrane electrode assembly for the fuel cell as described in 14 above which is sandwiched by separators.
16. A fuel cell, comprising two or more of the cells for the fuel battery as described in 15 above being laminated one on another.
Further, the present invention also relates to a vapor-grown carbon fiber as follows:
17. A vapor-grown carbon fiber, being characterized by having on its surface a physical site capable of carrying a catalyst metal.
18. The vapor-grown carbon fiber as described in 17 above, wherein the physical site is a defect generated by a chemical and/or physical action.
19. The vapor-grown carbon fiber as described in 18 above, wherein the physical action is an action by an impact and/or shearing force.
Hereinafter, the present invention will be described in detail.
A vapor-grown carbon fiber to be used as a carrier of a catalyst carrier of the present invention has an average outer diameter of from 2 to 500 nm and has been subjected to a crushing treatment so as to have a BET specific surface area of from 4 to 500 m2/g and an aspect ratio of from 1 to 200. Preferably, the average outer diameter is from 15 to 200 nm; the BET specific surface area is from 10 to 200 m2/g; and the aspect ratio is from 2 to 150. Further, preferably, an average fiber length is from 2 to 100 μm. By using as a carrier the vapor-grown carbon fiber which has been subjected to the crushing treatment so as to have properties within the respective ranges as described above, when a catalyst metal is carried thereon, the carrier is capable of carrying the catalyst metal while being in a state of particles having a small diameter and a large specific surface area and, as a result, a catalytic activity can be enhanced.
The crushing treatment has preferably been performed such that an average fiber length after the treatment becomes 0.8 or less when the average fiber length before the treatment is taken as 1. Further, the crushing treatment has preferably been performed such that a BET specific surface area after the treatment becomes 1.1 or more and, more preferably, 1.4 or more, when the BET specific surface area before the treatment is taken as 1.
The vapor-grown carbon fiber to be used in the present invention preferably contains a branched carbon fiber, and thereby an electric conductive pass of the carbon fiber is formed and, accordingly, electric conductivity as the catalyst carrier can be enhanced.
The vapor-grown carbon fiber to be used in the present invention is prepared by subjecting a fine carbon fiber produced by a vapor phase method to a crushing treatment. Performing the crushing treatment enables to produce a fine carbon fiber having a multi-layer structure, which comprises a discontinuous surface of a graphene sheet having a fracture surface at an end portion of the fiber; a continuous surface formed by combining an end portion of at least one graphene sheet with an end portion of an adjacent graphene sheet; and a hollow space in a center axis. By such a structure as described above, electric resistance of the carbon fiber is reduced and electric conductivity as a catalyst carrier is enhanced.
Characteristics of the fine carbon fiber are described with reference to
As shown in a schematic vertical cross-sectional diagram according to
On the other hand, as shown in a schematic cross-sectional diagram according to
The carbon fiber according to
The carbon fiber according to
Each of
In
In
In
Each of
The continuous surface which exists in the same surface as the fracture surface shows a surface in which a defect is generated in the graphene sheet laminated by thermal chemical vapor deposition and, accordingly, the graphene sheet has lost the regularity and is combined with an adjacent graphene sheet; or a fracture end of a graphene sheet is recombined with an end of another graphene sheet by a high temperature treatment of 2000° C. or more. A curved portion of the continuous surface comprises one or more of graphene sheets; however, in a case in which the number of the laminated graphene sheets is small, namely, in a case in which a curvature radius of such curved graphene sheets is small, the fiber is hard to stably exist since a surface energy of the curved portion is large, and therefore, the number of the laminated graphene sheets at the curved portion is preferably three more, more preferably five or more and, particularly preferably, five to ten.
The vapor-grown carbon fiber used in the present invention can be produced by crushing a vapor-grown carbon fiber produced by a vapor phase method and, preferably, a carbon fiber comprising a branched carbon fiber (produced by a method as described in, for example, JP-A-2002-266170 (WO02/49412)).
The vapor-grown carbon fiber to be used in such production can ordinarily be obtained by thermally decomposing an organic compound while using an organic transition metal compound as a catalyst. The organic compound which can serve as a raw material for the carbon fiber is a compound selected from among toluene, benzene, naphthalene, gases such as ethylene, acetylene, ethane, a natural gas, carbon monoxide and the like and mixtures thereof. Thereamong, aromatic hydrocarbons such as toluene and benzene are preferred. The organic transition metal compound is an organic compound containing a transition metal which can be a catalyst, specifically, any one of metals belonging to the groups IV to X in the periodic table. Particularly, compounds such as ferrocene and nickelocene are preferred.
The carbon fiber is, preferably, a carbon fiber in which an interlayer distance (d002) of a hexagonal carbon layer (002) by an X-ray diffractometry is 0.345 nm or more, a ratio (Id/Ig) of a peak height (Id) of the band at 1341 to 1349 cm−1 to a peak height (Ig) of the band at 1570 to 1578 cm−1 in a Raman scattering spectrum is 1 or more. In this case, Id denotes a broad band region corresponding to an increase of irregularity of a carbon structure, while Ig denotes a relatively sharp band region associated with a perfect graphite structure.
Raw materials to be crushed can be subjected to a thermal treatment at 600 to 1300° C. in order to remove an organic substance such as tar attached on a surface of the carbon fiber obtained by thermal decomposition.
As for crushing methods, a rotary crusher, a high-speed mill, a ball mill, a medium stirring mill, which adopts a method of crushing the fiber using an impact force, a jet crusher and the like can be utilized. Particularly, a vibrating mill such as a circular vibrating mill, a gyratory vibrating mill or a centrifugal mill is preferred. As for crushing media, ceramics balls of alumina, zirconia, silicon nitride and the like, or metal balls of stainless steel and the like can be used. Among these, stainless steel balls which can be removed by a high-temperature thermal treatment are preferred.
Further, it is advantageous to perform a dry type crushing in the absence of water and/or an organic solvent, since it is not necessary to perform a post-treatment step such as removing a dispersant after the crushing, drying the solvent or crushing a dry coagulated fiber.
The crushing is preferably performed in an atmosphere having an oxygen concentration of 5% by volume or more. By allowing oxygen to be present in a volume of 5% or more, a surface of a crushed carbon fiber is modified, to thereby facilitate a catalyst metal to be carried. The crushing is preferably performed in the air.
Further, in a pretreatment or a post-treatment of the crushing, a graphitization treatment can be performed for the purpose of enhancing electric conductivity of the vapor-grown carbon fiber. The graphitization treatment can be performed by carrying out a thermal treatment at 2000 to 3000° C. in an atmosphere of an inert gas.
The catalyst carrier according to the present invention comprises a crushed vapor-grown carbon fiber and a catalyst metal for promoting an oxidation-reduction reaction carried on the carbon fiber.
Catalyst metals for promoting the oxidation-reduction reaction are at least one element selected from the group consisting of transition metals belonging to the groups IV and V in the periodic table comprising platinum and other platinum metal elements or mixtures thereof, preferably, platinum metal elements (nickel, palladium and platinum) or an alloy containing these metal elements.
A method for carrying the catalyst metal on the crushed vapor-grown carbon fiber is not particularly limited and is performed by, for example, a liquid phase reduction method. An example in which fine platinum particles are carried on the crushed vapor-grown carbon fiber by the liquid reduction method is described below.
Firstly, the crushed carbon fiber is dispersed in a distilled water and a pH value of the resultant dispersion is adjusted by using, for example, sodium carbonate. A dispersion operation can be performed by, for example, an ultrasonic wave treatment while confirming a dispersion condition by, for example, visual observation. Since the vapor-grown carbon fiber is high in hydrophobicity, it is preferable to enhance hydrophilicity by performing a surface treatment (hereinafter, referred to also as “hydrophilization treatment”) on the carbon fiber in advance and, by this treatment, a specific surface area of the catalyst metal to be carried can be improved. The surface treatment can be performed in, for example, an acid solution (such as an aqueous nitric acid solution) for one to ten hours at 60 to 90° C.
To the resultant carbon fiber dispersion, an aqueous solution of chloroplatinic acid is added, thoroughly stirred and, then, an excess amount of a reducing agent such as formaldehyde is added to allow a reaction to proceed and, thereafter, a solid article is recovered by filtration. By drying the thus-recovered solid article in an atmosphere of an inert gas such as argon at 120 to 500° C., a catalyst carrier can be obtained in which platinum fine particles are carried on the vapor-grown carbon fiber.
The catalyst carrier according to the present invention is a catalyst carrier in which fine catalyst metal particles are carried on a vapor-grown carbon fiber as a carrier and has an improved catalyst activity per unit amount of the catalyst metal compared with a case in which a carrier in powder form such as carbon black is used. Further, by using the vapor-grown carbon fiber subjected to a crushing treatment, a grain diameter of the catalyst metal particles to be carried comes to be apparently small compared with a case in which the crushing treatment is not performed (namely, the specific surface area of the catalyst metal comes to be large). Specifically, it is possible to allow an average grain diameter of the catalyst metal to be carried to be 15 nm or less and, further, 10 nm or less, which enables to enhance the catalyst activity of the catalyst support and to obtain favorable characteristics for use in the electrode catalyst for the fuel cell.
The catalyst carrier according to the present invention can be applied for an electrode material, a membrane electrode assembly for a fuel battery, a cell for a fuel battery and a fuel battery and these articles can be produced by a known method.
The electrode material according to the present invention can be produced by forming a catalyst layer containing the above-described catalyst carrier on an electrically conductive base material such as carbon paper, carbon fiber woven fabric or carbon non-woven fabric. Formation of the catalyst layer can be performed by, for example, applying a slurry containing the catalyst carrier on an electrically conductive base material and, then, drying the resultant base material. The membrane electrode assembly for the fuel cell according to the present invention can be produced by thermally press-adhering the above-described electrode material comprising a gas diffusion layer and a catalyst layer on both surfaces of an electrolyte membrane. In a case in which the fuel cell is of a solid polymer type, the electrolyte membrane comprises a polymer material and, for example, a perfluorosulfonic acid type polymer can be used. A fuel cell can be prepared by sandwiching the membrane electrode assembly by separators having electric conductivity and two or more layers of such cell units are laminated one on another, to thereby prepare a fuel cell stack having a high output. Further, in order to suppress a leakage of an inner gas, it is also possible to provide a gasket between the electrolyte material and each of the separators.
Hereinafter, the present invention will specifically be described with reference to representative examples; however, these examples are given for an illustrative purpose only and by no means limit the invention.
Further, a ratio of an average fiber length was determined by obtaining average fiber lengths before and after carbon fibers were subjected to a crushing treatment in a cross-sectional photograph of carbon fibers by a transmission electron microscope (TEM). Further, a specific surface area was measured in accordance with a BET method which is an ordinary measuring method of the specific surface area by using a specific surface area measuring apparatus “NOVA-1200” manufactured by Yuasa-Ionics Co., Ltd.
5 g of vapor-grown carbon fiber having an average outer diameter of 150 nm, a specific surface area of 13 m2/g and an average fiber length of 10 μm was loaded in a rotary crusher (stainless steel-made crushing blade, rotation rate: 25000 rpm) and subjected to a crushing treatment for 10 minutes. Thereafter, a specific surface area and an average fiber length of the carbon fiber were measured and, as a result, the specific surface area and the average fiber length were 18 m2/g and 7.5 μm, respectively, which were 1.6 times and 0.75 times the original values, respectively. 0.2 g of the thus-crushed vapor-grown carbon fiber was dispersed in 50 ml of distilled water, 0.172 g of sodium carbonate was added and then, stirred with heat at 80° C. To the resultant dispersion, an aqueous solution containing 0.135 g of chloroplatinic acid was added dropwise, stirred for two hours and, then, a 35% aqueous solution of formaldehyde was added dropwise. After stirred for one hour, the resultant solution was filtered and, then, a solid material was subjected to a drying treatment for two hours at 400° C. in an atmosphere of argon, to thereby obtain a catalyst carrier in which a platinum grain was carried on a carbon fiber. A transmission electron microscope (TEM) photograph thereof is shown in
Further, diameters of the platinum catalyst were measured by observing the TEM photograph, to thereby obtain a distribution of the diameters. As a result, an average diameter of the platinum catalyst particles was 8 nm.
5 g of vapor-grown carbon fiber having an average outer diameter of 150 nm, a specific surface area of 13 m2/g and an average fiber length of 10 μm was loaded in a rotary crusher (stainless steel-made crushing blade, rotation rate: 25000 rpm) and subjected to a crushing treatment for 20 minutes. Thereafter, a specific surface area and an average fiber length of the carbon fiber were measured and, as a result, the specific surface area and the average fiber length were 24 m2/g and 6.0 μm, respectively, which were 1.8 times and 0.6 times the original values, respectively. 0.2 g of the thus-crushed vapor-grown carbon fiber was dispersed in 50 ml of distilled water, 0.172 g of sodium carbonate was added and then, stirred with heat at 80° C. To the resultant dispersion, an aqueous solution containing 0.135 g of chloroplatinic acid was added dropwise, stirred for two hours and then, a 35% aqueous solution of formaldehyde was added dropwise. After stirred for one hour, the resultant solution was filtered and, then, a solid material was subjected to a drying treatment for two hours at 400° C. in an atmosphere of argon, to thereby obtain a catalyst carrier in which platinum particles were carried on a carbon fiber. A TEM photograph thereof is shown in
Further, diameters of the platinum catalyst were measured by observing the TEM photograph, to thereby obtain a distribution of the diameters. As a result, an average diameter of the platinum catalyst particles was 5 nm.
5 g of vapor-grown carbon fiber having an average outer diameter of 150 nm, a specific surface area of 13 m2/g and an average fiber length of 10 μm was loaded in a rotary crusher (stainless steel-made crushing blade, rotation rate: 25000 rpm) and subjected to a crushing treatment for 10 minutes. Thereafter, a specific surface area and an average fiber length of the carbon fiber were measured and, as a result, the specific surface area and the average fiber length were 18 m2/g and 7.5 μm, respectively, which were 1.6 times and 0.75 times the original values, respectively. 0.2 g of the thus-crushed vapor-grown carbon fiber was, after being heated in a 60% aqueous solution of nitric acid for five hours at 70° C., dispersed in 50 ml of distilled water, 0.172 g of sodium carbonate was added and the dispersion was stirred with heat at 80° C. To the resultant dispersion an aqueous solution containing 0.135 g of chloroplatinic acid was added dropwise, stirred for two hours and then, a 35% aqueous solution of formaldehyde was added dropwise. After stirred for one hour, the resultant solution was filtered and, then, a solid material was subjected to a drying treatment for two hours at 400° C. in an atmosphere of argon, to thereby obtain a catalyst carrier in which platinum particles were carried on a carbon fiber. A TEM photograph thereof is shown in
Further, diameters of the platinum catalyst were measured by observing the TEM photograph, to thereby obtain a distribution of the diameters. As a result, an average diameter of the platinum catalyst particles was 6 nm.
5 g of vapor-grown carbon fiber having an average outer diameter of 150 nm, a specific surface area of 13 m2/g and an average fiber length of 10 μm was loaded in a rotary crusher (stainless steel-made crushing blade, rotation rate: 25000 rpm) and subjected to a crushing treatment for 20 minutes. Thereafter, a specific surface area and an average fiber length of the carbon fiber were measured and, as a result, the specific surface area and the average fiber length were 24 m2/g and 6.0 μm, respectively, which were 1.8 times and 0.6 times the original values, respectively. 0.2 g of the thus-crushed vapor-grown carbon fiber was, after being heated in a 60% aqueous solution of nitric acid for five hours at 70° C., dispersed in 50 ml of distilled water, 0.172 g of sodium carbonate was added and the dispersion was stirred with heat at 80° C. To the resultant dispersion an aqueous solution containing 0.135 g of chloroplatinic acid was added dropwise, stirred for two hours and then, a 35% aqueous solution of formaldehyde was added dropwise. After stirred for one hour, the resultant solution was filtered and, then, a solid material was subjected to a drying treatment for two hours at 400° C. in an atmosphere of argon, to thereby obtain a catalyst carrier in which platinum particles were carried on a carbon fiber. A TEM photograph thereof is shown in
Further, diameters of the platinum catalyst were measured by observing the TEM photograph, to thereby obtain a distribution of the diameters. As a result, an average diameter of the platinum catalyst particles was 3 nm.
Same operations were performed as in Example 1 except that the crushing treatment was not performed, to thereby obtain a catalyst carrier in which platinum particles were carried on the carbon fiber. A TEM photograph thereof is shown in
Same operations were performed as in Example 3 except that the crushing treatment was not performed, to thereby obtain a catalyst carrier in which platinum particles were carried on the carbon fiber. A TEM photograph thereof is shown in
Carbon black available in the market (under the name of Vulcan XC-72R manufactured by Cabot Inc. having a specific surface area of 230 m2/g) was used as it was. 0.2 g thereof was, after being heated for five hours at 70° C. in a 60% aqueous solution of nitric acid, dispersed in 50 ml of distilled water, sodium carbonate was added and the dispersion was stirred with heat at 80° C. An aqueous solution containing 0.135 g of chloroplatinic acid was added dropwise thereto, and the resultant dispersion was stirred for two hours and then, a 35% aqueous solution of formaldehyde was added dropwise. After stirred for one hour, the resultant solution was filtered and then, a solid material was subjected to a drying treatment for two hours at 400° C. in an atmosphere of argon, to thereby obtain a catalyst carrier in which platinum particles were carried on carbon black. A TEM photograph thereof is shown in
Further, diameters of the platinum catalyst were measured by observing the TEM photograph, to thereby obtain a distribution of the diameters. As a result, an average diameter of the platinum catalyst particles was 2 nm.
Each of the catalyst carriers prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 was mixed with a NAFION solution and the resultant mixture was applied on a carbon electrode, and an electrochemical measurement was performed by using the resultant electrode.
Activity per unit amount of a catalyst metal was evaluated from Tafel plots determined by an absolute value of a current density, a logarithmic number of the current density and a potential at a given voltage measured by a slow scan voltamogram (SSV). A 3-electrode type battery was used in an experiment, wherein a glassy carbon electrode was used as a working electrode, a platinum electrode as a counter electrode, and a hydrogen electrode as a reference electrode.
As for a measurement condition, a current value was measured while a voltage was changed from 1.2 V to 0.4 V at a scanning rate of 1 mV/sec. In order to standardize the thus-measured current values to be a current density (mA/cm2), a surface area of the electrode was obtained by using a cyclic voltammetry. The measurement of the surface area of the electrode was conducted with reference to a method as described in Denkikagaku Sokuteiho (Electrochemical Measuring Method) (Vol. I), Gihodo Shuppan Co., Ltd., p 88.
Results are shown in Table 2. The order of the absolute values of the current density at a voltage of 0.5 V in Examples was as follows: Example 2>Example 1>Example 3=Example 4>Comparative Example 1=Comparative Example 2>>Comparative Example 3.
Further, Tafel plots determined by a logarithmic number of current density at a voltage of from 0.82 V to 0.94 V and the voltage are shown in
| Number | Date | Country | Kind |
|---|---|---|---|
| 2004-018879 | Jan 2004 | JP | national |
This is an application filed pursuant to 35 U.S.C. Section 111(a) with claiming the benefit of U.S. Provisional application Ser. No. 60/541,505 filed Feb. 4, 2004 under the provision of 35 U.S.C. Section 111(b), pursuant to 35 U.S.C. Section 119(e) (1).
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