The present invention relates to an electrode catalyst production system and production method.
The operating temperature of a so-called polymer electrolyte fuel cell (Polymer Electrolyte Fuel Cell: referred to as “PEFC” hereunder if necessary) is about room temperature to 80° C. Further, a PEFC can be made lighter in weight because inexpensive commodity plastics or the like may be employed as a material(s) compositing the fuel cell main body. Furthermore, a PEFC can have its solid polymer electrolyte membrane made thinner so that the electric resistance can be lowered whereby a loss in power generation can be reduced relatively easily. In this way, since a PEFC has many advantages, it can be applied to fuel-cell automobiles, cogeneration systems for household use and the like.
As an electrode catalyst for a PEFC, there is known, for example, an electrode catalyst with platinum (Pt) or a platinum (Pt) alloy as an electrode catalyst component being supported on carbon as a support. When using such electrode catalyst as an electrode catalyst for a fuel cell, if the electrode catalyst contains a large amount of impurities derived from the raw materials thereof and/or impurities mixed thereinto from a production facility thereof, there may not be achieved a satisfactory catalytic activity, and corrosion of the catalytic layer may occur such that the life of the fuel cell may be shortened. Thus, it is preferred that the impurity content in the electrode catalyst be kept low. Here, examples of the impurities include chemical species belonging to the halogens (e.g. ions and salts thereof), and organic matters (organic acids, salts thereof, and condensates of organic acids).
For example, for the purpose of keeping a halogen content, particularly a chlorine content of the electrode catalyst low, there may be performed a step of eliminating chlorine after producing an electrode catalyst precursor as a raw material of the electrode catalyst. For example, the disclosure in Patent document 1 is such that a second catalyst metal precursor solution is to be mixed with a first catalyst metal precursor mixture and a carbon-based support mixture, followed by adjusting pH, repeating a heating and cooling procedure, washing a catalyst thus obtained with a centrifugal separator 3 to 4 times, and then drying the same with a freeze drier. Further, in Patent documents 2 and 3, as a wet dechlorination method for an ultrafine particulate titanium dioxide that can be utilized in a fuel cell catalyst, there is listed a method where titanium dioxide is to be suspended in water, and chlorine that has transferred to liquid phase is then separated from the system by filter press.
As is the case in Patent document 1, if using a centrifugal separator to wash an electrode catalyst precursor, the electrode catalyst precursor will adhere to the inner wall of the chamber in the centrifugal separator due to the centrifugal force, so that an operator will have to manually scratch off the adhering electrode catalyst.
Further, for example, in order to sufficiently eliminate the chlorine component contained in an electrode catalyst precursor, washing and filtration by water has to be repeated; for example, it may take at least 2 to 4 days to wash and filtrate 10 to 50 kg of a catalyst with one centrifuge. In this way, washing by a centrifugal separator takes time and effort, and has thus presented a problem of being inefficient.
Further, in Patent documents 2 and 3, although filter press is used for dechlorination of a fuel cell catalyst, there are no specific descriptions on for example a specific configuration and steps of a device for carrying out filter press, as well as conditions for washing and filtration steps.
The present invention was made in view of these circumstances, and is to provide an electrode catalyst production system and production method capable of drastically reducing the time and effort to produce an electrode catalyst, by omitting the operation for an operator to scratch off an electrode catalyst precursor, and by shortening the washing time of the electrode catalyst precursor
In order to solve such problem(s), the present invention provides an electrode catalyst production system for producing an electrode catalyst. The system includes:
an electrode catalyst precursor production device for producing an electrode catalyst precursor as a raw material of an electrode catalyst containing an electrically conductive support and a catalyst particle supported on the electrically conductive support;
a washing device for washing the electrode catalyst precursor by filter press; and
a drying device for drying the washed electrode catalyst precursor that has been washed by the washing device,
wherein the washing device has executors for executing:
a plate closing step for forming a filter chamber by clamping together filter plates;
an injection step for injecting a liquid containing the electrode catalyst precursor into the filter chamber from a stock liquid supply tube so as to filtrate the liquid, and then discharging a filtrate from filtrate discharge outlets;
a normal washing step for supplying a washing water from the stock liquid supply tube to the filter chamber, allowing the washing water to pass through a cake containing the electrode catalyst precursor, and then discharging the washing water from the filtrate discharge outlets;
a reverse washing step for supplying a washing water from the filtrate discharge outlets to the filter chamber, allowing the washing water to pass through the cake containing the electrode catalyst precursor, and then discharging the washing water from the filtrate discharge outlets which are different from the filtrate discharge outlets from which the washing water is supplied;
a plate opening step for opening the filter plates forming the filter chamber; and
a cake peeling step for bringing down a filter cloth so as to peel and drop the cake containing the electrode catalyst precursor, and
wherein in the injection step, the cake is formed in such a manner that a thickness thereof falls into a range that has been previously and experimentally determined in consideration of a washing degree and a washing time that are required for the electrode catalyst precursor used.
In the case of the aforesaid electrode catalyst production system, when the electrically conductive support is a conductive carbon, the thickness of the cake containing the electrode catalyst precursor may be 5 to 10 mm at the time of the injection step.
In the case of the aforesaid electrode catalyst production system, the washing device may further have an executor for executing a filter cloth washing step for washing the filter cloth with a washing water after the cake peeling step.
In the case of the aforesaid electrode catalyst production system, a washing time in the reverse washing step and a washing time in the normal washing step may be of similar length.
Further, the present invention provides an electrode catalyst production method for producing an electrode catalyst. The method includes:
an electrode catalyst precursor producing step for producing an electrode catalyst precursor as a raw material of an electrode catalyst containing an electrically conductive support and a catalyst particle supported on the electrically conductive support;
a washing step for washing the electrode catalyst precursor by filter press; and
a drying step for drying the washed electrode catalyst precursor that has been washed in the washing step,
wherein the washing step includes:
a plate closing step for forming a filter chamber by clamping together filter plates;
an injection step for injecting a liquid containing the electrode catalyst precursor into the filter chamber from a stock liquid supply tube so as to filtrate the liquid, and then discharging a filtrate from filtrate discharge outlets;
a normal washing step for supplying a washing water from the stock liquid supply tube to the filter chamber, allowing the washing water to pass through a cake containing the electrode catalyst precursor, and then discharging the washing water from the filtrate discharge outlets;
a reverse washing step for supplying a washing water from the filtrate discharge outlets to the filter chamber, allowing the washing water to pass through the cake containing the electrode catalyst precursor, and then discharging the washing water from the filtrate discharge outlets which are different from the filtrate discharge outlets from which the washing water is supplied;
a plate opening step for opening the filter plates forming the filter chamber; and
a cake peeling step for bringing down a filter cloth so as to peel and drop the cake containing the electrode catalyst precursor, and
wherein in the injection step, the cake is formed in such a manner that a thickness thereof falls into a range that has been previously and experimentally determined in consideration of a washing degree and a washing time that are required for the electrode catalyst precursor used.
In the case of the aforesaid electrode catalyst production method, when the electrically conductive support is a conductive carbon, the thickness of the cake containing the electrode catalyst precursor may be 5 to 10 mm at the time of the injection step.
In the case of the aforesaid electrode catalyst production method, the washing step may further have a filter cloth washing step for washing the filter cloth with a washing water after the cake peeling step.
In the case of the aforesaid electrode catalyst production method, a washing time in the reverse washing step and a washing time in the normal washing step may be of similar length.
In the case of the electrode catalyst production system and production method of the present invention, the operation for an operator to scratch off the electrode catalyst precursor can be omitted, and the washing time of the electrode catalyst precursor can be shortened, thus making it possible to drastically reduce the time and effort for producing an electrode catalyst having a low halogen content, particularly a low chlorine content.
With reference to the drawings, described hereunder are preferable embodiments of the electrode catalyst production system and production method of the present invention.
The electrode catalyst precursor production device 12 is to produce the electrode catalyst precursor as the raw material of the electrode catalyst 1. The electrode catalyst precursor production device 12 includes a reaction step executor 21 for executing a reaction step for producing the electrode catalyst precursor. In the reaction step, the electrode catalyst precursor as the raw material of the electrode catalyst 1 is produced by supporting catalyst components (core part 4, shell part 5) of the electrode catalyst 1 on a support 2 (see
The washing device 13 is to wash the electrode catalyst precursor produced by the electrode catalyst precursor production device 12 via filter press. At such washing device 13, not only the washing of the electrode catalyst precursor is carried out, but filtration and dewatering are also carried out as well.
An outline of a flow for performing washing by filter press is described (see
As shown in the block diagram of
The plate closing step S21 is a step for forming the filter chamber 112 by clamping together the filter plates 111, 111′, and is executed by the plate closing step executor 31.
The injection step S22 is a step for injecting the electrode catalyst precursor-containing liquid (stock liquid) 30 into the filter chamber 112 from a stock liquid supply tube 114 so as to filtrate the liquid, and then discharging the filtrate 42 from filtrate discharge outlets 115, 115′; the injection step S22 is executed by the injection step executor 32.
Further, in this injection step S22, the electrode catalyst precursor-containing cake 40 is formed in such a manner that the thickness thereof falls into a range that has been experimentally determined in advance. The thickness of the cake 40 is previously and experimentally determined in consideration of a washing degree and a washing time that are required for the electrode catalyst precursor used.
Here, if the electrode catalyst used employs a conductive carbon as its support, it is preferred that a thickness T of the cake 40 at the time of the injection step S22 be adjusted to 5 to 10 mm. When the thickness T of the cake 40 is not larger than 10 mm, there can be relatively easily achieved a sufficient washing effect by adjusting a washing time in the later-described normal washing step and/or reverse washing step. When the thickness T of the cake 40 is larger than 10 mm, there will be observed a greater tendency where a sufficient washing effect cannot be achieved even by extending the washing time in the later-described normal washing step and/or reverse washing step.
Further, when the thickness T of the cake 40 is not smaller than 5 mm, cracks are unlikely to be formed in the cake, and there will thus be observed a greater tendency for preventing the formation of a path(s) through which a washing water passes by without passing through the cake when flowing from a surface of the cake on the upstream side toward a surface thereof on the downstream side.
The normal washing step S23 is a step for supplying a washing water 43 from the stock liquid supply tube 114 to the filter chamber 112, allowing the washing water 43 to pass through the electrode catalyst precursor-containing cake 40, and then discharging the washing water 43 from the filtrate discharge outlets 115, 115′; the normal washing step S23 is executed by the normal washing step executor 33.
In the normal washing step S23, while performing washing, it is preferred that the temperature of the washing water 43 be switched at the moment when the electric conductivity p of the filtrate has reached a value that is as large as or smaller than a given value. For example, at the moment when the electric conductivity ρ of the filtrate has reached a value that is as large as or smaller than the given value, the washing water 43 may be switched from a normal temperature water (e.g. 23° C.) to a heated water (e.g. 70° C.). It is preferred that the given value of the electric conductivity ρ of the filtrate be a value selected from a range of 20 to 40 μS/cm. The temperature of the normal temperature water is preferably 20 to 25° C. The temperature of the heated water is preferably 60 to 80° C.
The reverse washing step S24 is a step for supplying the washing water 43 from the filtrate discharge outlet(s) 115 to the filter chamber 112, allowing the washing water 43 to pass through the electrode catalyst precursor-containing cake 40, and then discharging the washing water 43 from the filtrate discharge outlet(s) 115′ which are different from the filtrate discharge outlet(s) 115 from which the washing water 43 is supplied; the reverse washing step S24 is executed by the reverse washing step executor 34.
In the reverse washing step S24, while washing can be performed with a normal temperature water (e.g. 23° C.), it is preferred that washing be performed with a heated water (e.g. 70° C.) from the very start since the electric conductivity ρ of the filtrate will have already decreased to a certain extent at the end of the normal washing step S23. The temperature of the heated water is preferably 60 to 80° C.
The plate opening step S25 is a step for opening the filter plates 111, 111′ forming the filter chamber 112, and is executed by the plate opening step executor 35.
The cake peeling step S26 is a step for bringing down the filter cloth so as to peel and drop the electrode catalyst precursor-containing cake 40 that has been dewatered; the cake peeling step S26 is executed by the cake peeling step executor 36.
The filter cloth washing step S27 is a step for washing the filter cloth 113 with the washing water 43 after the cake peeling step S26, and is executed by the filter cloth washing step executor 37.
Here, a compression step may be performed after the normal washing step S23 and/or after the reverse washing step S24. The compression step is a step for further compressing and dewatering the electrode catalyst precursor-containing cake 40, and is executed by a compression step executor (not shown).
Here, it is preferable to employ a configuration where the pressurized water 119 is to be drawn from the diaphragm 118 after the compression step is over, because there will be no more pressing by the diaphragm 118, and the filter cloth 113 being pressed by the diaphragm 118 can thus be easily peeled from the cake 40.
Moreover, in this compression step, there may be employed a configuration where a diaphragm (not shown) is also provided at the other filter plate 111. In such case, the pressurized water will also be injected into the diaphragm (not shown) provided on the filter plate 111 side, whereby the electrode catalyst precursor-containing cake 40 can then be compressed and dewatered. Even in this case, it is preferable to employ a configuration where the pressurized water is to be drawn from the diaphragm after the compression step is over, because there will be no more pressing by the diaphragm (not shown), and the filter cloth 113 being pressed by the diaphragm (not shown) can thus be easily peeled from the cake 40.
In the above descriptions, one dewatering device 104 is described; in the case of the washing device 13 shown in
Treatment conditions such as a normal washing time in the normal washing step S23 and a reverse washing time in the reverse washing step S24 are adjusted such that the electric conductivity ρ of the filtrate obtained after the normal washing step S23 and/or after the reverse washing step S24 will be as large as or smaller than a predetermined value when measured by the JIS-standard testing method (JIS K0522). For example, the washing effect is enhanced if the washing time in the reverse washing step and the washing time in the normal washing step are of similar length. “Similar” refers to a notion that there may be a difference of 0 to 15 min (an absolute value of a difference between the washing time in the normal washing step and the washing time in the reverse washing step). Further, the filtrate is the liquid discharged from the filtrate discharge outlet(s) after performing washing, and it is preferred that there be used all the filtrates discharged in such step.
The predetermined value of the electric conductivity ρ of the filtrate obtained after the normal washing step S23 is preferably a value selected from a range of not larger than 20 μS/cm. The predetermined value of the electric conductivity ρ of the filtrate obtained after the reverse washing step S24 is preferably a value selected from a range of not larger than 10 μS/cm. When the electric conductivity ρ of the filtrate is not larger than 10 μS/cm, the concentration of the chlorine (Cl) and bromine (Br) species contained in the electrode catalyst precursor shall be reduced to such a degree that the electrode catalyst can be put to practical use as an electrode catalyst for use in a fuel cell.
As the washing water 43 used in the washing device 13, while a pure water such as an ultrapure water may be used, it does not necessarily have to be a pure water. For example, there may be used an ion-exchange water or the like having a pH of 6 to 8 and an electric conductivity ρi of smaller than 10 μS/cm when measured by the JIS-standard testing method (JIS K0522).
The drying device 14 serves to dry the washed electrode catalyst precursor 41 that has been washed by the washing device 13. The drying device 14 includes a drying step executor 51 for executing a drying step for drying the washed electrode catalyst precursor 41 that has been washed by the washing device 13. As a drying method in the drying step, other than a conventional drying method where a vacuum shelf dryer or the like (not shown) is used to vacuum dry a crushed electrode catalyst precursor put on shelves, there may also be employed a drying method using, for example, RIBOCONE (not shown) and a PV mixer (not shown).
There are no particular restrictions on the structure of the electrode catalyst produced in the present embodiment; it will suffice if the electrode catalyst has a structure where noble metal catalyst particles are supported on an electrically conductive support (e.g. conductive carbon support, conductive metal oxide support). For example, the electrode catalyst may be a so-called Pt catalyst, a so-called Pt alloy catalyst (e.g. PtCo catalyst, PtNi catalyst), and a so-called core-shell catalyst having a core-shell structure.
For example, as for a core-shell catalyst having a composition where palladium is employed as a constituent element for the core part 4, and platinum is employed as a constituent element for the shell part 5, chlorine (Cl) species-containing materials such as chloride salts of platinum (Pt) and chloride salts of palladium (Pd) are used as raw materials in many cases. By means of the electrode catalyst production system and production method of the present embodiment, there can be produced an electrode catalyst having a reduced content of these chlorine (Cl) species.
One example of the structure of an electrode catalyst is described in greater detail with reference to the drawings; as shown in
That is, the electrode catalyst 1 has the catalyst particle 3 supported on the support 2; this catalyst particle 3 has a structure where the core part 4 serves as a core (core), and the shell part 5 serves as a shell coating the surface of the core part 4. Further, the constituent element (chemical composition) of the core part 4 and the constituent element (chemical composition) of the shell part 5 differ from each other in composition.
A specific example of a core-shell structure is further shown hereunder; in
In the present embodiment, chlorine (Cl) species refer to chemical species containing chlorine as a constituent component element. Specifically, chlorine-containing chemical species may include chlorine atoms (Cl), chlorine molecules (Cl2), chloride ions (Cl−), chorine radicals (Cl·), polyatomic chlorine ions, and chlorine compounds (e.g. X—Cl where X is a counterion).
In the present embodiment, bromine (Br) species refer to chemical species containing bromine as a constituent component element. Specifically, bromine-containing chemical species may include bromine atoms (Br), bromine molecules (Bra), bromide ions (Br−), bromine radicals (Br·), polyatomic bromine ions, and bromine compounds (e.g. X—Br where X is a counterion).
As shown in
As shown in
Working examples listed below are to exemplify the embodiment of the present invention, and shall not be construed as limiting the scope of the present invention.
As a precursor of the electrode catalyst precursor, there was produced a precursor of a Pt particle-supported carbon catalyst (referred to as “Pt/C catalyst” hereunder; produced by N.E. CHEMCAT CORPORATION; Pt carrying rate 50 wt %; product name: “SA50BK”).
As a support of this precursor, there was used a commercially available conductive hollow carbon support {produced by Lion Corporation; product name “CARBON ECP” (registered trademark) (Ketjenblack EC300J); specific surface area 750 to 800 m2/g}. By adding a water-soluble reductant to a water containing this support and a water-soluble Pt salt, and then allowing a reduction reaction of the Pt component to progress at a given temperature, the electrode catalyst precursor used in the present embodiment was prepared.
The liquid containing the electrode catalyst precursor obtained as above was dispersed in a kettle without being dried, and was used as a stock liquid to be treated by the washing device.
The liquid containing the electrode catalyst precursor obtained in the production example 1 was introduced into the washing device so as to perform the washing treatment. Table 1 shows a treatment time(s) of each step with regard to the washing device. At first, the injection step was performed for 20 min. The thickness of the electrode catalyst precursor-containing cake in the injection step was set to 5 to 10 mm.
Such thickness of the cake is within a thickness range previously determined by a preliminary experiment in view of the washing degree and washing time that are required for the electrode catalyst precursor used.
Next, the normal washing step was performed. In the normal washing step, treatment was at first performed with a washing water of a normal temperature (23° C.) for 24 min; the washing water was then switched to a heated water (70° C.) at the moment when the electric conductivity p of the filtrate had reached 40 μS/cm or lower; and treatment was then performed with such heated water for another 50 min. After the normal washing step, the compression step was performed for 5 min. Next, the reverse washing step was performed; in the reverse washing step, treatment was performed with a heated washing water (70° C.) for 73 min. The washing treatment was performed for about 2.9 hours in total.
An ion-exchange water was used as the washing water. The ion-exchange water used exhibited an electric conductivity ρi of 7.70 μS/cm when at a normal temperature (23° C.), and an electric conductivity ρi of 4.6 μS/cm when heated (70° C.).
The electrode catalyst precursor-containing cake obtained after the treatment by the washing device was then treated with the drying device at a temperature of 70° C. in the air for 24 hours so as to be dried, thereby obtaining the electrode catalyst.
The liquid containing the electrode catalyst precursor obtained in the production example 1 was introduced into the washing device so as to perform the washing treatment. Table 1 shows a treatment time(s) of each step with regard to the washing device. At first, the injection step was performed for 40 min. The thickness of the electrode catalyst precursor-containing cake in the injection step was set to 11 to 15 mm.
Such thickness of the cake is out of a thickness range previously determined by a preliminary experiment in view of the washing degree and washing time that are required for the electrode catalyst precursor used.
Next, the normal washing step was performed. In the normal washing step, treatment was at first performed with a washing water of a normal temperature (23° C.) for 33 min; the washing water was then switched to a heated water (70° C.) at the moment when the electric conductivity p of the filtrate had reached 40 μS/cm or lower; and treatment was then performed with such heated water for another 60 min. After the normal washing step, the compression step was performed for 5 min, and the reverse washing step was performed subsequently. However, since the conductivity p of the filtrate did not change from the electric conductivity ρ of the filtrate that was observed at the time when the normal washing step was finished, the treatment was then stopped after performing the reverse washing step for 36 min i.e. after performing the washing treatment for about 2.9 hours in total.
An ion-exchange water was used as the washing water. The ion-exchange water used exhibited an electric conductivity ρi of 7.70 μS/cm when at a normal temperature (23° C.), and an electric conductivity ρi of 4.6 μS/cm when heated (70° C.).
The electrode catalyst precursor-containing cake obtained after the treatment by the washing device was then treated with the drying device at a temperature of 70° C. in the air for 24 hours so as to be dried, thereby obtaining the electrode catalyst.
The liquid containing the electrode catalyst precursor obtained in the production example 1 was introduced into a centrifugal separator so as to be subjected to a washing treatment. Washing was repeated until the electric conductivity ρ of the filtrate had reached 10 μS/cm or lower when measured by JIS-standard testing method (JIS K0522). A dispersion liquid was then prepared by dispersing the electrode catalyst precursor obtained into an ultrapure water, followed by filtrating such dispersion liquid. The residue obtained by filtration was then treated with the drying device at a temperature of 70° C. in the air for 24 hours so as to be dried, thereby obtaining the electrode catalyst.
As shown in Table 1, in the working example 1, while the electric conductivity ρ of the filtrate at the time when the normal washing step was finished was 15.9 μS/cm, the electric conductivity ρ of the filtrate at the time when the reverse washing step was finished had dropped to 9.7 μS/cm. The electric conductivity ρ of the filtrate was able to be reduced to 10 μS/cm or lower in a washing treatment time of less than 3 hours. In contrast, in the comparative example 1, while the electric conductivity ρ of the filtrate at the time when the normal washing step was finished had dropped to 19.3 μS/cm, the conductivity did not decrease at all from 19.3 μS/cm thereafter even by performing the reverse washing step. Further, in the comparative example 2 where a centrifugal separator was used to perform washing as is the conventional case, 15 to 19 hours were required in order for the electric conductivity ρ of the filtrate to be reduced to 10 μS/cm or lower, as a result of conducting the comparative example three times. Table 2 shows and compares the treatment times in the working example 1 and the comparative example 2. In Table 2, there are separately shown a treatment time from raw material feed to solid-liquid separation; and a time required for cake washing and dewatering.
Thus, in the case of the electrode catalyst production system and production method of the present embodiment, the time required for the treatment (washing step) by the washing device can be drastically reduced to ⅕ or shorter as compared to the conventional treatment using a centrifugal separator. Further, as for the washing device of the present embodiment, since the electrode catalyst precursor-containing cake is to be automatically peeled, there can be omitted the operation for an operator to scratch off the electrode catalyst precursor, thereby making it possible to also drastically save effort.
The present invention has so far been described with reference to the embodiment and working example thereof; the invention may be variously modified before exploitation. Especially, there are no particular restrictions on the electrode catalyst precursor production device 12 (reaction step, electrode catalyst precursor producing step S1) and the drying device 14 (drying step S3), and various modified examples may be employed. Further, even in the case of the washing device 13, the structure thereof shall not be limited to that shown in
In the case of the electrode catalyst production system and production method of the present invention, the operation for an operator to scratch off the electrode catalyst precursor can be omitted, and the washing time of the electrode catalyst precursor can be shortened, thus making it possible to drastically reduce the time and effort for producing an electrode catalyst having a low halogen content, particularly a low chlorine content.
Thus, the present invention relates to an electrode catalyst production system and production method that are applicable not only to the electric equipment industry manufacturing fuel cells, fuel-cell automobiles, mobile phones and the like, but also to ene-farms, cogeneration systems and the like; the invention contributes to developments related to the energy industry and environmental technologies.
Number | Date | Country | Kind |
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2020-050941 | Mar 2020 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2021/012058 | 3/23/2021 | WO |