CN104549233A - Preparation method of fuel cell anode catalyst - Google Patents
Preparation method of fuel cell anode catalyst Download PDFInfo
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- CN104549233A CN104549233A CN201410614702.9A CN201410614702A CN104549233A CN 104549233 A CN104549233 A CN 104549233A CN 201410614702 A CN201410614702 A CN 201410614702A CN 104549233 A CN104549233 A CN 104549233A
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Abstract
The invention discloses a preparation method of a fuel cell anode catalyst. The preparation method comprises the following steps: (1) adding chloroplatinic acid and surfactants into deionized water; dropwise adding sodium borohydride aqueous solution while stirring at the same time to form stable nano-platinum particle sol; (2) putting a carbon nano tube into the deionized water and stirring for 10-20 minutes, wetting by using absolute ethyl alcohol, and adding certain quantity of deionized water, heating and boiling to obtain washed active carbon nano tube samples; performing acid pickling and alkali pickling to obtain an activated carrier; (3) ultrasonically dispersing the active carrier which is treated in the step (2) by using the deionized water and adding the processed active carrier into the prepared platinum particle sol; filtering, washing and neutralizing; grinding into powder to obtain a primary catalyst; (4) dispersing the primary catalyst obtained in the step (3) into the deionized water, and adding into the chloroplatinic acid and the surfactant solution which are prepared additionally; dropwise adding sodium borohydride solutions, filtering, washing and drying in vacuum to obtain the fuel cell anode catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of fuel battery anode catalyst.
Background technology
Fuel cell has caused the great attention of countries in the world as the green energy resource of 21 century.Wherein proton membrane fuel battery (PEMFC), the research of direct methanol fuel cell (DMFC) more makes one notice.One of their advantage is the power supply that can be widely used as destination.But, no matter Proton Exchange Membrane Fuel Cells or direct methanol fuel cell, all there is CO to Pt catalyst poisoning problem, because containing a small amount of CO in reformed gas, also the intermediate gas of similar CO is had in methanol oxidation process, and the CO of trace can make the performance of battery significantly decline, therefore, solve anti-CO problem and become countries in the world fuel cell studies circle problem anxious to be resolved.
Due to hydrogen be fuel Proton Exchange Membrane Fuel Cells technical barrier---the storaging and transport technology of hydrogen is not well solved so far, people attempt to develop to have the direct liquid fuel battery that the liquid state of electro-chemical activity or the rich hydrogen compound of solution state are fuel always.Hydrogen is replaced directly to input fuel cell power generation methyl alcohol---direct methanol fuel cell is extensively studied for many years, although its required platinum catalyst used adds several times than hydrogen-oxygen (sky) fuel cell, but unit are electrode generate electricity can power still only have the part of hydrogen-air fuel cell, and methyl alcohol is poisonous, there is potential safety hazard.Under this background, with nontoxic, do not fire, the accumulating direct borohydride fuel cell (DBFC) that boron hydride is fuel is easily subject to the people's attention and researchs and develops.It is with the alkaline solution of boron hydride (as NaBH4, KBH4) for fuel input anode, with oxygen or air for oxidant inputs negative electrode, is the device of electric energy by electrochemical means by chemical energy.
DBFC electrochemical reaction is:
Anode: BH4-+8OH-→ BO2-+6H2O+8e-E=-1.24V
Negative electrode: 2O2+4H2O+8e-→ 8OH-E=0.40V
Total cell reaction: BH4++2O2 → BO2++2H2O E=1.64V
The theoretical electromotive force of DBFC is 1.64V, all high than methyl alcohol (1.21V) and hydrogen (1.23V).Be that theoretical specific energy and the specific capacity of the direct sodium borohydride fuel cell of fuel reaches 9.30KWh/Kg and 5.67KAh/Kg, respectively far away higher than direct methanol fuel cell (theoretical specific energy and specific capacity are respectively 6.08KWh/Kg and 5.03KAh/Kg) with sodium borohydride.But because BH4-is easy to hydrolysis occurs at anode, what in fact BH4-was difficult to realize eight electrons oxidizes is stable into stream reaction.The actual anode oxidation reaction of BH4-can be represented by reaction equation below, and x wherein represents the electron number that each BH4-electro-oxidation reaction is released.
Anode:
How to suppress BH4-hydrolysis, promote that the reaction of its eight electrons oxidizes is the key problem in direct borohydride fuel cell research always, this is closely related with the character of anode catalyst.Current research shows, BH4-is approximately 8e reaction in the electroxidation on Au surface, and be 4e reaction on Ni surface, the electron number of Pt, Pd surface electrical oxidation correspondence is relevant with discharging condition, is 2 ~ 6e reaction.Consider from energy efficiency, be that anode catalyst is ideal with Au, therefore, forefathers have carried out more deep research to the performance taking gold as anode catalyst.Such as (the S C Amendola such as Amendola, P Onnerud, M T Kelly, et al.JPower Sources, 1999,84 (1): 130-133) with galvanoplastic gold-supported platinum alloy catalyst (97%Au+3%Pt) on charcoal cloth, particle size 500 ran, with it for anode, Pt/C is that negative electrode assembles direct sodium borohydride-air-fuel battery.Research shows: BH4-is approximately 7 electron reactions at the electro-oxidation reaction of this anode catalyst surface, the close 20mW/cm2 of the maximum power of battery under room temperature.(the M.H.Atwan such as Atwan, C.L.B.Macdonald, D.O.Northwood, et al.J.Power Sources, 2005,150:27-35) with carbon black Vxc-72R for carrier, traditional Bonneman colloid method is adopted to prepare nanoscale Au, Au-Pt (atomic ratio 1: 1) and Au-Pd (atomic ratio 1: 1) as anode catalyst, research after assembled battery shows: under room temperature, and the catalytic activity of three is followed successively by Au-Pt > Au > Au-Pd.The battery open circuit voltage of Au be 1.2V, Au-Pt be 1.0V.But the polarization performance of Au is poor, author thinks that Au-Pt alloy (particle size 6nm) demonstrates better dimensional effect than Au (particle size 10nm).(the H.Cheng such as Cheng, K.Scott.J.Power Sources, 2006, immersion reduction method 160:407-412) is adopted to reduce gold chloride with isopropyl alcohol, and prepare Au/C anode electrocatalyst through high-temperature calcination, take Pt/C as electrocatalyst for cathode, Nafion117 is direct sodium borohydride-oxygen fuel cell open circuit voltage 1.05V at room temperature of barrier film assembling, maximum power density 18mW/cm2.
From the research of forefathers, Au anode electrocatalyst used in direct borohydride fuel cell also exists complicated process of preparation, and gold grain size is large, and electro catalytic activity is lower, adds the problem that Pt, Pd noble metal increases catalyst cost.Therefore, exploitation preparation cost is low, small particle diameter, and the Au anode electrocatalyst of high catalytic activity is the key technology that direct borohydride fuel cell realizes needing in commercialization process to solve.
Although, disclosed in prior art and carried out in-situ reducing with reducing agent and prepare the method for fuel battery anode catalyst, but in the catalyst prepared of method described in the prior art, the bullion content that carrier supports is low, do not reach requirement, cause the catalytic efficiency of catalyst low; And the noble metal skewness on carrier, assemble noble metal nano particles in a large number, and peak portion is out exposed, have impact on the activity of catalyst greatly in tunnel.
Summary of the invention
The object of the invention is to the preparation method proposing a kind of fuel battery anode catalyst.
For reaching this object, the present invention by the following technical solutions:
A preparation method for fuel battery anode catalyst, comprises the following steps:
(1), precious metal solution is prepared: add in deionized water by chloroplatinic acid and surfactant, stirring makes it mix in 10 ~ 20 minutes, the sodium borohydride aqueous solution of fresh preparation is dripped under room temperature and magnetic agitation, dropwise and continue to stir 30-60 minute, form stable nano-platinum particle colloidal sol;
(2), carrier carries out activation processing; Carbon nano-tube is stirred 10-20 minute in deionized water, soaks with absolute ethyl alcohol, then add the heating of a certain amount of deionized water and boil, reflux 1 hour, filter, 80 DEG C of dryings 2 hours, obtain washing Activated Carbon Nanotubes sample; Pickling: the 10% salt acid dip 24 hours of the sample after washing, filters, and washing pH is 7,80 DEG C of vacuumizes 2 hours; Alkali cleaning: the carbon nano-tube of pickling to be carried out be dipped in the hydrogenperoxide steam generator of 5% 24 hours, filter, washing; 80 DEG C of vacuumizes; Obtain activated carrier;
(3), Kaolinite Preparation of Catalyst: move after the active carrier deionized water ultrasonic disperse that step (2) was processed and add the made platinum grain colloidal sol of step (1), stirring and adsorbing 24-48 hour, after filtration washing is neutrality to pH, filter cake was vacuum drying 2 hours, grind into powder, obtains preliminary catalytic agent;
(4), then the preliminary catalytic agent that step (3) obtains is distributed in deionized water, ultrasonic agitation 20-30 minute, adds in the chloroplatinic acid and surfactant solution configured in addition; Mix and blend 30-60 minute; Temperature controlled water baths 80 DEG C, drips sodium borohydride solution under stirring condition, and reacted rear continuation and stirred 30-60 minute, filtered, washing, vacuumize, obtains described fuel battery anode catalyst.
Described surfactant is the one in polyvinyl alcohol, polyethylene glycol, polyethylene glycol bilaurate and PDDA.
Described surfactant and the mass ratio of platinum are 0.5 ~ 5: 1, and the mass ratio of sodium borohydride and platinum is 0.5 ~ 5: 1, and in platinum colloidal sol, platinum concentration is 10ug/ml ~ 1mg/ml.
Beneficial effect of the present invention:
1, Pt nanoparticle is evenly distributed on carrier, present invention employs twice and supports, and first time supports and mainly adopts absorption method, and a large amount of nano particles trends towards concentrating on etc. to position; Second time adopts local reduction way, and on the basis of tunnel filling, nano particle platinum particles can be evenly distributed on carrier surface;
2, catalyst activity is high, not easy in inactivation;
3, preparation technology is simple, without the need to high-temperature calcination, is easy to produce in enormous quantities, has good prospects for commercial application;
4, the catalyst particle size of preparation is little, and dispersive property is excellent, has higher specific area.
Embodiment
Embodiment 1
1), precious metal solution is prepared: add in deionized water by chloroplatinic acid and surfactant, stirring makes it mix in 20 minutes, under room temperature and magnetic agitation, drip the sodium borohydride aqueous solution of fresh preparation, dropwise and continue stirring 60 minutes, form stable nano-platinum particle colloidal sol;
(2), carrier carries out activation processing; Carbon nano-tube is stirred 20 minutes in deionized water, soaks with absolute ethyl alcohol, then add the heating of a certain amount of deionized water and boil, reflux 1 hour, filter, 80 DEG C of dryings 2 hours, obtain washing Activated Carbon Nanotubes sample; Pickling: the 10% salt acid dip 24 hours of the sample after washing, filters, and washing pH is 7,80 DEG C of vacuumizes 2 hours; Alkali cleaning: the carbon nano-tube of pickling to be carried out be dipped in the hydrogenperoxide steam generator of 5% 24 hours, filter, washing; 80 DEG C of vacuumizes; Obtain activated carrier;
(3), Kaolinite Preparation of Catalyst: move after the active carrier deionized water ultrasonic disperse that step (2) was processed and add the made platinum grain colloidal sol of step (1), stirring and adsorbing 48 hours, after filtration washing is neutrality to pH, filter cake was vacuum drying 2 hours, grind into powder, obtains preliminary catalytic agent;
(4), then the preliminary catalytic agent that step (3) obtains is distributed in deionized water, ultrasonic agitation 30 minutes, adds in the chloroplatinic acid and surfactant solution configured in addition; Mix and blend 60 minutes; Temperature controlled water baths 80 DEG C, drips sodium borohydride solution under stirring condition, has reacted rear continuation stirring 60 minutes, filters, and washing, vacuumize, obtains described fuel battery anode catalyst.Described surfactant is polyvinyl alcohol; Described surfactant and the mass ratio of platinum are 5: 1, and the mass ratio of sodium borohydride and platinum is 5: 1, and in platinum colloidal sol, platinum concentration is 1mg/ml.
Embodiment 2
1), precious metal solution is prepared: add in deionized water by chloroplatinic acid and surfactant, stirring makes it mix in 10 minutes, under room temperature and magnetic agitation, drip the sodium borohydride aqueous solution of fresh preparation, dropwise and continue stirring 30 minutes, form stable nano-platinum particle colloidal sol;
(2), carrier carries out activation processing; Carbon nano-tube is stirred 10 minutes in deionized water, soaks with absolute ethyl alcohol, then add the heating of a certain amount of deionized water and boil, reflux 1 hour, filter, 80 DEG C of dryings 2 hours, obtain washing Activated Carbon Nanotubes sample; Pickling: the 10% salt acid dip 24 hours of the sample after washing, filters, and washing pH is 7,80 DEG C of vacuumizes 2 hours; Alkali cleaning: the carbon nano-tube of pickling to be carried out be dipped in the hydrogenperoxide steam generator of 5% 24 hours, filter, washing; 80 DEG C of vacuumizes; Obtain activated carrier;
(3), Kaolinite Preparation of Catalyst: move after the active carrier deionized water ultrasonic disperse that step (2) was processed and add the made platinum grain colloidal sol of step (1), stirring and adsorbing 24 hours, after filtration washing is neutrality to pH, filter cake was vacuum drying 2 hours, grind into powder, obtains preliminary catalytic agent;
(4), then the preliminary catalytic agent that step (3) obtains is distributed in deionized water, ultrasonic agitation 20 minutes, adds in the chloroplatinic acid and surfactant solution configured in addition; Mix and blend 30 minutes; Temperature controlled water baths 80 DEG C, drips sodium borohydride solution under stirring condition, has reacted rear continuation stirring 30 minutes, filters, and washing, vacuumize, obtains described fuel battery anode catalyst.Described surfactant is PDDA.The mass ratio of surfactant and platinum is 0.5: 1, and the mass ratio of sodium borohydride and platinum is 0.5: 1, and in platinum colloidal sol, platinum concentration is 10ug/ml.
Claims (3)
1. a preparation method for fuel battery anode catalyst, is characterized in that comprising the following steps:
(1), precious metal solution is prepared: add in deionized water by chloroplatinic acid and surfactant, stirring makes it mix in 10 ~ 20 minutes, the sodium borohydride aqueous solution of fresh preparation is dripped under room temperature and magnetic agitation, dropwise and continue to stir 30-60 minute, form stable nano-platinum particle colloidal sol;
(2), carrier carries out activation processing; Carbon nano-tube is stirred 10-20 minute in deionized water, soaks with absolute ethyl alcohol, then add the heating of a certain amount of deionized water and boil, reflux 1 hour, filter, 80 DEG C of dryings 2 hours, obtain washing Activated Carbon Nanotubes sample; Pickling: the 10% salt acid dip 24 hours of the sample after washing, filters, and washing pH is 7,80 DEG C of vacuumizes 2 hours; Alkali cleaning: the carbon nano-tube of pickling to be carried out be dipped in the hydrogenperoxide steam generator of 5% 24 hours, filter, washing; 80 DEG C of vacuumizes; Obtain activated carrier;
(3), Kaolinite Preparation of Catalyst: move after the active carrier deionized water ultrasonic disperse that step (2) was processed and add the made platinum grain colloidal sol of step (1), stirring and adsorbing 24-48 hour, after filtration washing is neutrality to pH, filter cake was vacuum drying 2 hours, grind into powder, obtains preliminary catalytic agent;
(4), then the preliminary catalytic agent that step (3) obtains is distributed in deionized water, ultrasonic agitation 20-30 minute, adds in the chloroplatinic acid and surfactant solution configured in addition; Mix and blend 30-60 minute; Temperature controlled water baths 80 DEG C, drips sodium borohydride solution under stirring condition, and reacted rear continuation and stirred 30-60 minute, filtered, washing, vacuumize, obtains described fuel battery anode catalyst.
2. method according to claim 1, is characterized in that described surfactant is the one in polyvinyl alcohol, polyethylene glycol, polyethylene glycol bilaurate and PDDA.
3. method according to claim 2, it is characterized in that the mass ratio of described surfactant and platinum is 0.5 ~ 5: 1, the mass ratio of sodium borohydride and platinum is 0.5 ~ 5: 1, and in platinum colloidal sol, platinum concentration is 10ug/ml ~ 1mg/ml.
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| CN201410614702.9A CN104549233A (en) | 2014-11-04 | 2014-11-04 | Preparation method of fuel cell anode catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707333A (en) * | 2019-10-08 | 2020-01-17 | 成都新柯力化工科技有限公司 | High-dispersity fuel cell catalyst slurry and preparation method thereof |
| CN113745542A (en) * | 2021-09-15 | 2021-12-03 | 北京化工大学 | High platinum loading platinum/carbon catalyst for fuel cell and preparation method thereof |
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2014
- 2014-11-04 CN CN201410614702.9A patent/CN104549233A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707333A (en) * | 2019-10-08 | 2020-01-17 | 成都新柯力化工科技有限公司 | High-dispersity fuel cell catalyst slurry and preparation method thereof |
| CN113745542A (en) * | 2021-09-15 | 2021-12-03 | 北京化工大学 | High platinum loading platinum/carbon catalyst for fuel cell and preparation method thereof |
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Application publication date: 20150429 |