CN104347885B - Electrode catalyst for fuel cell and its manufacture method, catalyst for fuel cell carry electrode and fuel cell - Google Patents

Electrode catalyst for fuel cell and its manufacture method, catalyst for fuel cell carry electrode and fuel cell Download PDF

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CN104347885B
CN104347885B CN201410377838.2A CN201410377838A CN104347885B CN 104347885 B CN104347885 B CN 104347885B CN 201410377838 A CN201410377838 A CN 201410377838A CN 104347885 B CN104347885 B CN 104347885B
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fuel cell
catalyst
noble metal
mentioned
base metal
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CN104347885A (en
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伊藤裕也
福永聪洋
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Suzuki Motor Corp
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Suzuki Motor Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

The usage amount that offer of the invention employs the Pt that can either be greatly reduced in PtCo alloys is obtained in that electrode catalyst for fuel cell and its manufacture method, catalyst for fuel cell carrying electrode and fuel cell with the PtCo/C of the equal above mass activity of Pt/C catalyst again.A kind of electrode catalyst for fuel cell, it is to carry alloy in carbon carrier, and the alloy includes noble metal and base metal, wherein, the mol ratio, i.e. base metal/noble metal ratio of the noble metal of above-mentioned alloy and base metal has been set as 4~9.

Description

Electrode catalyst for fuel cell and its manufacture method, catalyst for fuel cell hold Carry electrode and fuel cell
Technical field
The present invention relates to electrode catalyst for fuel cell and its manufacture method, catalyst for fuel cell carry electrode with And fuel cell.
Background technology
Using macromolecular material as electrolyte polymer electrolyte fuel cell (PEFC：polymer Electrolyte fuel cell) it is height output, and can easily be minimized, therefore it is mainly used for onboard power (example Such as, fuel-cell vehicle), fixation power supply etc..In recent years, various ground carry out for the purpose of the further high performance of PEFC Hair.
Currently, for the electrode catalyst of PEFC, platinum (Pt) is carried in carbon (C) carrier as carbon material Pt/C catalyst turns into main flow.But, platinum shows catalyst performance higher, is on the other hand but your gold of rare and costliness Category, therefore in order to manufacture PEFC more at low cost, seek the usage amount of the expensive platinum of reduction.
As one of electrode catalyst of usage amount of platinum can be reduced, carbon carrier can be set forth in and carry platinum-cobalt alloy (PtCo) platinum-cobalt alloy catalyst (PtCo/C catalyst).PtCo/C catalyst is because it is found that higher than Pt/C catalyst urges Agent activity (oxygen reduction reaction activity) this point and receive much concern.
Here, having been recorded in patent document 1, the mixing ratio (weight ratio) of preferably Pt and Co is Pt：Co=6：1~3：2. Record in addition, even if the ratio of assistant metal (Co) is improved, but catalyst activity can be reduced, and, in manufacturing process not It is alloyed but individually the generation ratio of assistant metal (Co) of carried is likely to increase (paragraph 0011).
And, being recorded in patent document 2, the mixing ratio (weight ratio) of preferably Pt and Co is Pt：Co=1：1~5：1.
In addition, having been recorded in patent document 3, the mixing ratio (mol ratio) of preferably Pt and Co is Pt：Co=2：1~9：1.
But, according to the record of 1~patent document of patent document 3, in the past, in PtCo/C catalyst, generally by Pt with The mixing ratio (mass ratio and mol ratio) of Co is set to Pt >=Co.
Its reason is envisioned for, and as described in patent document 1, main performance catalyst activity is platinum, if therefore The ratio of Co is improved, then catalyst activity reduction, and, the alloying of PtCo is not operatively carried out in manufacturing process, but The ratio of the Co for individually being carried by C carriers increases (paragraph 0011).
In addition, the usage amount that Pt can be reduced by improving the ratio of Co is recorded in patent document 1 and is reduced urging Advantage (paragraph 0011) as agent cost.But, although there is cost reduction, but there is catalyst activity drop Low shortcoming, even it is contemplated that can only also be set to Pt to greatest extent：Co=1：1.
That is, in the PtCo/C catalyst of reality, the usage amount of the Pt in PtCo alloys could not be both greatly reduced Desired catalyst activity is obtained again.
Patent document 1：Japanese Unexamined Patent Publication 2003-142112
Patent document 2：Japanese Unexamined Patent Publication 2005-129457
Patent document 3：Japanese Unexamined Patent Publication 2006-179427
The content of the invention
Problems to be solved by the invention
For above-mentioned situation, it is an object of the invention to provide employing the Pt that can either be greatly reduced in PtCo alloys Usage amount be obtained in that electrode catalyst for fuel cell with the PtCo/C of the equal above mass activity of Pt/C catalyst again And its manufacture method, catalyst for fuel cell carry electrode and fuel cell.
The scheme for solving problem
The present invention makes in order to achieve the above object, and it is a kind of electrode catalyst for fuel cell, and it is in carbon Alloy is carried on carrier, the alloy includes that by noble metal and base metal the electrode catalyst for fuel cell is characterised by, Noble metal and the mol ratio, i.e. base metal/noble metal ratio of base metal are 4~9 in above-mentioned alloy.
In addition, above-mentioned base metal/noble metal than represent manufacture when (during so-called blanking) mixing ratio.
Above-mentioned base metal/noble metal ratio more preferably 5~9, most preferably 7.Above-mentioned noble metal is preferably platinum, above-mentioned Base metal is preferably cobalt.
Another technical scheme of the invention is that a kind of catalyst for fuel cell carries electrode, the catalyst for fuel cell Carrying electrode includes the catalyst layer with above-mentioned electrode catalyst for fuel cell.And another technical scheme is a kind of fuel Battery, the fuel cell includes that above-mentioned catalyst for fuel cell carries electrode.
In addition, another technical scheme of the invention is a kind of manufacture method of electrode catalyst for fuel cell, its feature It is, including following operation：To addition hydrophilic polymer in the mixed solution containing noble metal precursor and base metal precursor Operation；The operation of impregnated carrier in mixed solution after above-mentioned addition；The carrier after above-mentioned dipping is carried out in nitrogen atmosphere The operation of heating；And the operation being fired to the carrier after above-mentioned heating in blanket of nitrogen；Contain above-mentioned noble metal precursor It is 4~9 with the mol ratio, i.e. base metal/noble metal ratio of the noble metal in the mixed solution of base metal precursor and base metal.
In addition, above-mentioned base metal/noble metal than represent manufacture when (during so-called blanking) mixing ratio.
The manufacture method of electrode catalyst for fuel cell of the invention in its embodiment, above-mentioned hydrophilic polymer It is at least a kind hydrophilic polymer selected from the group being made up of polyacrylic acid, PVP, polyvinyl alcohol.
The manufacture method of electrode catalyst for fuel cell of the invention in its embodiment, above-mentioned base metal/your gold Category ratio preferably 4~9, more preferably 5~9, most preferably 7.The manufacture of electrode catalyst for fuel cell of the invention In its embodiment, above-mentioned noble metal is preferably platinum to method, and above-mentioned base metal is preferably cobalt.
The effect of invention
Using the present invention again, using the teaching of the invention it is possible to provide the usage amount for employing the Pt that can either be greatly reduced in PtCo alloys can Obtain the electrode catalyst for fuel cell and its manufacture method, fuel of the PtCo/C of Pt/C catalyst twice above mass activities Battery catalyst carrier electrode and fuel cell.
Brief description of the drawings
Fig. 1 is the mass activity of the electrode catalyst for fuel cell for representing the PtCo/C for employing embodiments of the invention Curve map.
Specific embodiment
Hereinafter, electrode catalyst for fuel cell of the invention and its manufacture method, fuel electricity are illustrated in further detail Pond catalyst carrier electrode and the implementation method of fuel cell.
First, the manufacture method of electrode catalyst for fuel cell of the invention is illustrated.
In the manufacture method of electrode catalyst for fuel cell of the invention, at least perform to containing noble metal precursor with Impregnated carrier in operation, the mixed solution after above-mentioned addition of hydrophilic polymer is added in the mixed solution of base metal precursor Operation, the operation that is heated to the carrier after above-mentioned dipping in nitrogen atmosphere and in blanket of nitrogen to above-mentioned heating after The operation that carrier is fired.
In the manufacture method of electrode catalyst for fuel cell of the invention, regulation contains noble metal precursor and base metal The mixed solution of precursor.Preferably noble metal is platinum (Pt), and preferably base metal is cobalt (Co).
In regulation, mixed noble metal precursor and base metal precursor in a solvent.
Solvent is not particularly limited, for example, can use ultra-pure water, distilled water, ion exchange water etc., it is preferred to use Ultra-pure water.
In the implementation method that noble metal is set into platinum, platinum precursor is not particularly limited, for example, can be aoxidized using hexahydro Platinic acid (H2Pt(OH)6), the acid solution such as chloroplatinic acid, it is preferred to use hexahydro aoxidizes the acid solution of platinic acid.
Acid solution is not particularly limited, for example, can use nitric acid, hydrochloric acid etc., it is preferred to use nitric acid.
In the implementation method that base metal is set into cobalt, cobalt precursors are not particularly limited, for example, can use cobalt nitrate six Hydrate, cobalt chloride (II) etc., it is preferred to use Cobalt(II) nitrate hexahydrate.
In the manufacture method of electrode catalyst for fuel cell of the invention, contain above-mentioned noble metal precursor and base metal Noble metal and the mol ratio, i.e. base metal/noble metal ratio of base metal in the mixed solution of precursor are 4~9, more preferably 5~9, most preferably 7.
The above-mentioned operation of hydrophilic polymer is added in the mixed solution containing noble metal precursor and base metal precursor In, hydrophilic polymer is not particularly limited, preferably from by polyacrylic acid (PAA), PVP, polyvinyl alcohol structure Into group in select at least a kind hydrophilic polymer.As long as such polymer, it becomes possible to suppress the cohesion of cobalt particle.
In the case of using PAA, preferably the mean molecule quantity of PAA is 8000~12000 scope.The measurement of molecular weight Method can for example use gel permeation chromatography (GPC) etc..
In the case of using PAA, in the case of the mixed solution containing platinum precursor and cobalt precursors, the addition of PAA Relative to the Pt and the gross weight of Co in mixed solution, for example in Pt：Co=1：74wt%~93wt% is preferably when 7.That is, make Be to Pt and Co gross weight be denominator, the additions that represent of the weight % with the actual weight of PAA as molecule, be added To reach the scope of 74wt%~93wt%.
As long as such scope, it becomes possible to suppress catalyst particle cohesion, coarsening, energy in ablating work procedure described later Enough reduce the stripping quantity of the metal (platinum, cobalt) not being alloyed.It is preferred that in the case where making Co ratios increase/reduce, also making PAA Addition increase/reduce, conscientiously study after as a result, preferably as table 1 below setting range.
【Table 1】
Pt∶Co PAA additions wt%/(Pt+Co gross weights)
1∶1 25~32
1∶3 52~65
1∶5 66~82
1∶7 74~93
1∶9 80~100
The setting of table 1 is directed to Pt：Co ratios discretely show.But, ratio is taken in transverse axis (X-axis), in the longitudinal axis (Y-axis) Wt% is taken, will be coupled together between the wt% of the addition of lower end with line segment, with line segment by between the wt% of the addition of upper end Couple together, and obtain curve map, as long as obtaining wt% values from the curve map, it becomes possible to for Pt：Co ratios continuously obtain PAA Suitable addition.
In addition, the addition (upper end) of PAA can be obtained as so following.
(calculated example) 1：In the case of 7
＜ presses 1：It is situation ＞ that 100wt% is converted when 9
1：The discharge quantity of 9 Co：2.193g
1：The discharge quantity of 7 Co：2.037g
1：7 PAA additions=2.037/2.193 × 100 ≈ 93wt%
In the manufacture method of electrode catalyst for fuel cell of the invention, addition hydrophilic polymer operation it Afterwards, the operation of impregnated carrier in the mixed solution after hydrophilic polymer addition is implemented.Adjusted by the pH for carrying out mixed solution Section, so as to be carried the colloid of the base metals such as the noble metals such as platinum and cobalt as hydroxide by carrier.
As carrier, it is not particularly limited, for example, can uses carbon black, Ketjen black, CNT etc..
As the reagent used in being adjusted in pH, it is not particularly limited, as long as alkaline solution can just be used, example If using ammoniacal liquor etc..Thus, acid mixed solution is set to the alkalescence that pH value is about 10, makes the conduct in mixed solution Ion and the noble metal and base metal that exist are separated out as the hydroxide of noble metal and base metal on carrier.It is in noble metal In the case that platinum, base metal are cobalt, separated out on carrier as the hydroxide of platinum and cobalt.
In addition, the hydroxide by adding the base metals such as noble metal and cobalt such as above-mentioned PAA, the platinum in the mixed solution of alkalescence Thing is obtained in that good stability and dispersiveness.That is, the hydroxide of noble metal and base metal is with stabilization and scattered state Separated out on carrier.Thus, it is possible to suppress hydroxide dissolution in alkaline mixed solution of noble metal and base metal, therefore energy The hydroxide of noble metal and base metal is enough improved to the load-carry duty of carrier.
Carrier to carrying the hydroxide of noble metal and base metal filtered, clean after be vacuum dried. Specifically, for example, carrying out attraction filtering to the solution containing the carrier after carrying, cleaning is being sufficiently carried out using ultra-pure water Afterwards, the vacuum drying of 3 hours is carried out with 60 DEG C.
Then, the operation heated to above-mentioned dried carrier in nitrogen atmosphere is performed.Specifically, in nitrogen atmosphere In hydrogen reduction is carried out to the hydroxide of the base metals such as noble metal and cobalt such as the platinum that is carried by carrier.
Heating-up temperature is preferably 400 DEG C~500 DEG C of scope.In addition, the heat time is preferably the model of 2 hours~3 hours Enclose.
Then, the operation being fired to the carrier after above-mentioned heating in blanket of nitrogen is implemented.By above-mentioned hydrogen reduction and Fire, be obtained in that noble metal-base metal alloy catalyst as platinum-cobalt alloy catalyst (PtCo/C catalyst).Burn Temperature processed is preferably 600 DEG C~800 DEG C of scope.In addition, the firing time is preferably the scope of 3 hours~7 hours.
The firing can also be carried out in two stages.In this case, the firing temperature in the 1st ablating work procedure is preferably 700 DEG C~800 DEG C of scope, the firing time is preferably the scope of 0.5 hour~1 hour.In addition, the burning in the 2nd ablating work procedure Temperature processed is preferably 600 DEG C~700 DEG C of scope, and the firing time is preferably the scope of 2 hours~6 hours.
By adding the hydrophilic polymers such as above-mentioned PAA, so as to also remain the mixing in alkalescence in the ablating work procedure The good stability and dispersiveness that the hydroxides of the base metal such as the noble metals such as the platinum in solution and cobalt have.Accordingly, it is capable to Enough reduce the cohesion between noble metal-base metal alloy.Thus, the total surface area of noble metal-base metal alloy increases, can Obtain catalyst activity PtCo/C catalyst higher.
Pickling can also be carried out to the carrier fired in blanket of nitrogen.Because this can be in the metal not being alloyed (the mainly base metal such as cobalt) and impurities left on the carrier in the case of remove metal that this is not alloyed (mainly cobalt Deng base metal) and impurity.In addition, being filtered as described above to the carrier after pickling, being cleaned, being vacuum dried.
As pickle, it is not particularly limited, for example, can uses dust technology, dilute sulfuric acid etc..
By adding the hydrophilic polymers such as above-mentioned PAA, noble metal and the cobalt such as platinum in the mixed solution of alkalescence can be made Hydroxide Deng base metal obtains good dispersiveness, therefore noble metal and the hydroxide stabilization of base metal on carrier Change, and micronized.Thus, even if being fired at high temperature, platinum and cobalt will not also depart from from carrier, it is possible to increase PtCo/C The alloy rate of catalyst etc. (noble metal-base metal)/C.By improving alloy rate, even if carrying out pickling, it is also possible to relative In the stripping quantity in the past reducing the metal not being alloyed.
Such operation, is obtained in that the fuel cell electrode for carrying the base metals such as the noble metals such as platinum and cobalt more than Electrode catalyst.Obtained electrode catalyst for fuel cell is used, catalyst for fuel cell can be suitably produced and be held Carry electrode, fuel cell.
【Embodiment】
Hereinafter, show that embodiment etc. specifically describes the present invention, but the present invention is not limited to this.
Embodiment 1
Implement the manufacture method of electrode catalyst for fuel cell of the invention, the quality for obtaining obtained catalyst is lived Property.
In the case where noble metal to be set to platinum (Pt), base metal is set to cobalt (Co), before adjusting platinum precursor and cobalt The discharge quantity of body, so as in mol ratio " Pt：Co=1：PtCo/C alloy catalysts are modulated in the range of X, X=1~9 ".
Specifically, the total amount of the bearing capacity of the Pt+Co for carbon (C) is fixed as 30wt%, according to mole Than changing the discharge quantity of each precursor (platinum precursor and cobalt precursors), and modulate PtCo/C alloy catalysts.
The modulation of PtCo/C alloy catalysts
It is described below in mol ratio (Pt：Co=1：7) embodiment of modulation PtCo/C alloy catalysts is suitable in the case of Sequence.
Used as platinum precursor, (Tanaka is expensive for the hexahydro platinum oxide acid+nitric acid solution of 204g/L to have used platinum concentration at 20 DEG C Metal (Co., Ltd.) is made), as cobalt precursors, use cobalt nitrate (II) hexahydrate (and Wako Pure Chemical Industries (Co., Ltd.) System, purity 99.5%).
4.7249ml platinum precursor and 10.059g cobalt precursors are mixed in 500ml ultra-pure waters, mixed solution is obtained.
In the mixed solution for being obtained, the gross weight addition 74 relative to the Pt in mixed solution and Co (is pressed into Co ratios Rate conversion=10wt% × 10.059/1.355) wt% polyacrylic acid (PAA) solution (and Wako Pure Chemical Industries (Co., Ltd.) 25%) system, concentration about and stir.
To 7g carbon ECP is added, stirred in the mixed solution, (lion king (Co., Ltd.) makes, Ketjen black, specific surface area： 800m2/ g) as carrier.
Then, ammoniacal liquor (and Wako Pure Chemical Industries (Co., Ltd.) system, superfine, concentration 25%) is diluted to 1/100, will be diluted Ammoniacal liquor afterwards is dripped in the mixed solution that with the addition of carrier, is adjusted such that pH value turns into 10.
Afterwards, it is sufficiently carried out filtering, cleans, and is dried 12 hours using vacuum drier.
The hydrogen reduction of two hours is carried out to the carrier for obtaining with 500 DEG C in nitrogen atmosphere.
Afterwards, two firing in stage (the 1st ablating work procedures are carried out in blanket of nitrogen：800 DEG C, 0.5 hour；2nd fires work Sequence：600 DEG C, 6 hours).
Pickling is carried out to the carrier after firing using dust technology (and Wako Pure Chemical Industries (Co., Ltd.) are made, superfine), is gone forward side by side Row filtering, cleaning, vacuum drying, obtain platinum-cobalt alloy catalyst (PtCo/C catalyst).
In addition, the weight rate of the Pt in the mixed solution containing platinum precursor with cobalt precursors and Co, i.e. Pt/Co ratios are set as 7.
On other mol ratios (Pt：Co=1：X situation), is also carried out modulation holding with the Pt+Co that is carried carbon (C) The total amount of carrying capacity is set to 30wt%, and other are identical, so as to obtain platinum-cobalt alloy catalyst (PtCo/C catalyst).
The evaluation of mass activity
By using rotating disc electrode (RDE：Rotating Disk Electrode) method cyclic voltammetry (CV) measurement Platinum-cobalt alloy catalyst (PtCo/C catalyst) to being obtained as above is evaluated.
Measure under the following conditions, the mass activity of PtCo/C catalyst is obtained according to the current value under 0.85V [mA/mg-Pt cm2, the mass activity when reference potential relative to RHE (reversible hydrogen electrode) is 0.85V].In addition, quality Activity refers to the redox reaction activity of every 1g platinum (Pt).
Electrolyte：0.1M HClO4(high chloro acid solution)
Rotating speed：1600rpm、
Sweep speed：10mV/s
Temperature：25℃
Use machine：
Rotating disc electrode device (DYNAMIC ELECTRODE) HR-301 Big Dipper electrician's systems
Controller (DYNAMIC ELECTRODE CONTROLLER) HR-502 Big Dipper electrician's systems
Potentiostat HZ-7000 Big Dipper electrician's systems
The evaluation result of mass activity is represented in the graph of figure 1.In addition, by conventional Pt/C catalyst (Tanakas Noble metal system, TEC10E50E.Hereinafter referred to as conventional Pt/C catalyst.) mass activity urged as Pt on the market Agent is indicated.
In the case of Co/Pt=1~9
First, PtCo/C catalyst of the invention is obtained in that the quality more than equal with conventional Pt/C catalyst is lived Property.
In the case of Co/Pt=4~9
As long as within the range, for PtCo/C catalyst of the invention, it becomes possible to which Pt usage amounts (g) is set in the past Pt/C catalyst less than half, further, it is possible to obtain and conventional Pt/C catalyst it is equal more than mass activity.
In the case where load-carry duty (metal ratio that support C is carried) is 30wt.%, for 1g Pt/C catalyst, Pt Content is 0.3g.
For 1g PtCo/C (Pt：Co=1：4 situation) alloy catalyst, Pt contents are 0.136g.
Pt usage amounts slip now turns into the ≈ of (0.3-0.136) × 100/0.3 55%, significantly reduces.
In the case of Co/Pt=5~9
In the case of the scope, PtCo/C catalyst of the invention is obtained in that more than conventional Pt/C catalyst twices Mass activity.
In the case of Co/Pt=7
Under this condition, PtCo/C catalyst of the invention is obtained in that the mass activity of maximum.
As being obtained in that in the present embodiment, break former common technical knowledge, even if in Co/Pt=1~9 In the range of also obtain excellent mass activity.
In addition, the present inventor thoroughly finds out, by adding polyacrylic acid (PAA) in the operation of " premodulated ", so that Pt Hydroxide and Co hydroxide are improved to the load-carry duty of carbon (C) carrier, therefore catalyst activity improves (Japanese Patent Application 2013- 068935).In addition, the present inventor also thoroughly finds out, because PtCo is easy to alloying and the raising of alloy rate, therefore catalyst is lived Property improve (Japanese Patent Application 2013-068935).
As more than, according to the present invention, the usage amount of Pt can either be greatly reduced, it is also possible to obtain and Pt/C catalysis Mass activity more than agent is equal.

Claims (9)

1. a kind of fuel cell manufacture method of platinum cobalt electrode catalyst, it is characterised in that including following operation：
To the operation that hydrophilic polymer is added in the mixed solution containing noble metal precursor and base metal precursor；
The operation of impregnated carrier in mixed solution after above-mentioned addition；
The operation heated to the carrier after above-mentioned dipping in nitrogen atmosphere；And
The operation being fired to the carrier after above-mentioned heating in blanket of nitrogen；
Mol ratio, the i.e. low-priced gold of noble metal and base metal in the mixed solution containing above-mentioned noble metal precursor and base metal precursor Category/noble metal ratio is 4~9,
Above-mentioned hydrophilic polymer is polyacrylic acid, and above-mentioned noble metal is platinum, and above-mentioned base metal is cobalt,
It is denominator, the actual weight with polyacrylic acid for the gross weight to the platinum in the mixed solution after above-mentioned addition and cobalt For the value that the weight % of molecule is represented, its scope is set as following table,
Pt∶Co PAA additions wt%/(Pt+Co gross weights) 1∶1 25~32 1∶3 52~65 1∶5 66~82 1∶7 74~93 1∶9 80~100
And, ratio is taken in transverse axis (X-axis), wt% is taken in the longitudinal axis (Y-axis), will be connected between the wt% of the addition of lower end with line segment Pick up and, will be coupled together between the wt% of the addition of upper end with line segment, and obtain curve map, poly- third is obtained from the curve map The wt% of olefin(e) acid, is modulated into the mixed solution of the polyacrylic acid containing the addition tried to achieve.
2. the fuel cell according to claim 1 manufacture method of platinum cobalt electrode catalyst, it is characterised in that
Above-mentioned base metal/noble metal ratio is 5~9.
3. the fuel cell according to claim 1 and 2 manufacture method of platinum cobalt electrode catalyst, it is characterised in that
Above-mentioned base metal/noble metal ratio is 7.
4. the fuel cell that a kind of manufacture method of the fuel cell platinum cobalt electrode catalyst described in utilization claim 1 is obtained With platinum cobalt electrode catalyst, it is characterised in that
The fuel cell platinum cobalt electrode catalyst carries alloy on the carbon carrier, and the alloy includes noble metal and base metal, Noble metal and the mol ratio, i.e. base metal/noble metal ratio of base metal are 4~9 in above-mentioned alloy.
5. fuel cell according to claim 4 platinum cobalt electrode catalyst, it is characterised in that
Above-mentioned base metal/noble metal ratio is 5~9.
6. fuel cell according to claim 4 platinum cobalt electrode catalyst, it is characterised in that
Above-mentioned base metal/noble metal ratio is 7.
7. the platinum cobalt electrode catalyst of the fuel cell according to any one of claim 4~6, it is characterised in that
Above-mentioned noble metal is platinum, and above-mentioned base metal is cobalt.
8. a kind of catalyst for fuel cell carries electrode, wherein,
The catalyst for fuel cell carries electrode to be included with the fuel cell electrode any one of claim 4~7 The catalyst layer of electrode catalyst.
9. a kind of fuel cell, wherein,
The fuel cell includes that the catalyst for fuel cell described in claim 8 carries electrode.
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