CN102380400B - Core-shell structural anode catalyst for direct borohydride fuel cells and preparation method thereof - Google Patents
Core-shell structural anode catalyst for direct borohydride fuel cells and preparation method thereof Download PDFInfo
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Abstract
Disclosed are a core-shell structural anode catalyst for direct borohydride fuel cells and a preparation method thereof. The catalyst comprises Mcore-Aushell nano composite particles which utilize M as the core and utilizes Au as the shell, and the particle size of the Mcore-Aushell particles ranges from 10nm to 50nm. The preparation method includes steps: firstly, adding M-salt and a stabilizing agent into a solvent sequentially, introducing nitrogen gas into the solvent and then stirring and heating the solvent, introducing and stirring nitrogen gas again, dropping a reducing agent to realize reaction and obtain M-nano catalyst sol, and then obtaining M-nano particles after filtering and washing; secondly, dissolving the M-nano particles into solvent, adding stabilizing agent and introducing nitrogen gas into the solvent along with stirring, adding chloroauric acid-tetrahydrofuran solution, introducing nitrogen gas again, dropping reducing agent to realize reaction and prepare nano-catalyst sol, separating and washing the nano-catalyst sol, drying the nano-catalyst sol in vacuum, and finally preparing powdered Mcore-Aushell nano-particle catalyst by means of grinding. The core-shell structural anode catalyst for direct borohydride fuel cells has higher BH4 (tetrahydrobiopterin)-oxidation activity and is low in hydrogen evolution, and accordingly fuel utilization rate is improved.
Description
Technical field
What the present invention relates to is a kind of direct borohydride fuel cell eelctro-catalyst, and specifically a kind of nuclear shell structure nano compound particle, as the direct borohydride fuel cell anode material, belongs to electro-catalysis technology and energy technology field.
Background technology
Direct borohydride fuel cell (Direct Borohydride Fuel Cell, DBFC) is a kind of use liquid alkali metal boron hydride ABH
4(A=Na, Li or K) is the TRT of fuel.Because alkali metal borohydride is a kind of hydrogeneous more and stable hydrogeneous anion substance again, its hydrogen storage ability is similar to methyl alcohol, but because carbon elements not more " cleans " than methyl alcohol; The volume energy density of sodium borohydride liquid fuel (about 3000Ah/L) is greater than liquified hydrogen (about 2000Ah/L), and its weight energy density (about 5Ah/g) is much larger than metal hydride (about 0.7Ah/L); With methyl alcohol, compare, the boron hydride stable chemical nature, be easy to store supply, uses safe and nonflammable.So use the direct borohydride fuel cell that the alkali metal borohydride aqueous solution is fuel to be expected to become the power supply that solves a low temperature decentralized fuel storage difficult problem, cheap.
DBFC adds alkali metal borohydride in corresponding alkali lye as liquid fuel, in the anode-side oxidation, discharges 8 electronics; Oxidant (oxygen, air or hydrogen peroxide) is passed in identical alkali lye, reduce at cathode side.Its anodic oxidation reactions is:
BH
4 - + 8OH
- = BO
2 - + 6H
2O + 8e
- （1）
Yet in the actual discharge process, BH
4 -always there is hydrolysis in various degree on electrode:
Due to BH on electrode
4 -electro-oxidation reaction and BH
4 -hydrolysis vie each other, therefore the combined reaction metering-type is written as:
BH
4 - + nOH
- = BO
2 - + (n-2)H
2O + (4 -0.5n)H
2 +ne
- (3)
expression is by each BH
4 -ion is the actual apparent electron number discharged on anode, and its size is relevant with electrode material and reaction condition, usually is less than theoretical value 8, BH
4 -the electron number produced in the DBFC anode oxidation process, lower than 8, has not only reduced faradic efficiency, and the bubble hydrogen discharged can hinder the migration of ion and reduce the performance of battery, and the operation of simultaneously returning battery brings certain potential safety hazard.
The anode electrocatalysis material that DBFC is used at present, mainly contain precious metals pt, Pd and Au, non-noble metal Ni, Cu and some hydrogen storage materials and alloy etc.In these electrode catalytic materialses, according to BH
4release hydrogen whether in catalytic oxidation process, be divided into electrode material " catalysis " and " on-catalytic " two classes.BH
4electrochemical oxidation reactions on " catalysis " materials such as Pt, Pd, Ni, Cu has higher catalytic activity, but the catalytic activity of its hydrolysis is also very high, therefore faradic efficiency is lower; And BH
4on these " on-catalytic " electrodes of Au, Ag, although can obtain very high electron number
n, but its oxidizing reaction rate is slow.Therefore, some researchers adopt method preparation " difunctional " catalyst of alloying, attempt to develop both to BH
4the electrochemical oxidation reactions activity is high, simultaneously the anode catalyst of catalyzing hydrolysis not again.(the Atwan M H such as document Atwan, Macdonald C L B, Northwood D O, Gyenge E L. J. Power Sources, 2006,158 (1): 36-44) adopt the Bonneman colloid method to prepare carbon-supported nano Au, Au-Pt and Au-Pd catalyst, under room temperature, three's catalytic activity is followed successively by Au-Pt>Au>Au-Pd, this shows to add the Pt of " catalysis " can improve NaBH in the Au of " on-catalytic "
4oxidation activity.Although adopt the method for binary metal alloying can improve catalytic electrode material to NaBH
4oxidation activity, but in alloy electrode material, " catalysis " metal component contacts with electrolyte, releasing hydrogen gas still, fuel availability is lower, so the performance of alloying electrode catalyst still can not meet the needs of direct borohydride fuel cell.
Summary of the invention
The objective of the invention is provides a kind of high performance nucleocapsid structure M that has for direct borohydride fuel cell
core-Au
shellnano-complex particle anode electrocatalyst and preparation method, solve the problem that existing DMFC anode activity is low, the hydrolysis liberation of hydrogen is serious, fuel availability is low.
For realizing this purpose, the present invention is achieved through the following technical solutions:
The nuclear shell structure nano metallic has the performance of shell and inner nuclear material concurrently, can also produce compound collaborative multifunctional effect simultaneously.The present invention is kernel by adopting " catalysis " metal, the nucleocapsid structure M that the Au of take is shell
core-Au
shellnano-complex particle, as the direct borohydride fuel cell anode catalyst, can not only keep gold to BH
4the characteristics that catalytic hydrolysis reaction speed is little, and can avoid " catalysis " material directly to contact with electrolyte, performance " catalysis " material is to BH
4the active high characteristics of catalytic oxidation.This bimetallic nuclear shell type nano meter particle, interior nuclear element produces inductive effect to the d orbital electron of shell Au metal, structure and the combination that can effectively change shell metallic d orbital electron can, the adsorption of nucleocapsid structure catalysis material is changed, thereby improve the catalytic oxidation activity of surface crust Au.
Direct borohydride fuel cell anode catalyst of the present invention is that M, shell are the nucleocapsid structure M that Au forms by kernel
core-Au
shellnano-complex particle, the particle diameter 10 ~ 50nm of core-shell particles.
The preparation method of direct borohydride fuel cell anode catalyst of the present invention comprises the following steps:
(1) prepare the M particle: M-salt and stabilizing agent are added in the 100ml solvent successively, and stirring logical nitrogen fully mix it in 20 ~ 30 minutes, then are heated to 50 ~ 80 ℃, continue to pass into nitrogen and constantly stir, and dripping concentration is 0.3 molL
-1reducing agent, adding the reducing agent mole is 1.2 ~ 2.5 times of M element, rate of addition is 40 min
-1, react 20 ~ 60 min, prepare M nanocatalyst colloidal sol, then suction filtration, with the distilled water washing, obtain the M nano particle;
(2) by the M nano particle in above-mentioned (1), again be dissolved in solvent, add stabilizing agent under stirring, the concentration of stabilizing agent is 0.5 ~ 5g/L, pass into nitrogen and stir 30 minutes, the ratio that is 0.5 ~ 2.0:1 according to M, Au atomic molar ratio again adds the tetrahydrofuran solution that concentration is the 0.3g/L gold chloride, constantly stir at 60 ~ 70 ℃ of temperature and continue to pass into nitrogen, then with 20 ~ 30 min
-1speed to drip concentration be 0.1 molL
-1reducing agent, the mol ratio of reducing agent and gold atom is 2.5:1, continue stirring reaction 2h at 60 ~ 70 ℃ of temperature, make nanocatalyst colloidal sol, then centrifugation, by the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours, 300 ~ 400 ℃ of heat treatment 1h in the tube furnace argon gas atmosphere, grinding can obtain Powdered M
core-Au
shellthe core-shell structure nanometer particle catalyst.
In the preparation method of above-mentioned catalyst with core-casing structure, M-salt used is NiCl
26H
2o, CoCl
26H
2o, Cu (NO
3) 3H
2o, H
2ptCl
66H
2o, PdCl
22H
2o and Pd (NO
3)
22H
2a kind of in O, the concentration of M-salt in solvent is 5 ~ 30mmol/L.
In the preparation method of above-mentioned catalyst with core-casing structure, solvent used is a kind of in ethylene glycol, water, oxolane, isopropyl alcohol and ethanol.
In the preparation method of above-mentioned catalyst with core-casing structure, stabilizing agent used is a kind of in polyethylene arsenic pyrrolidone (PVP), four octyl group ammonium bromides, polyethylene glycol and polyvinyl alcohol, and stabilizing agent concentration in solvent is 0.5 ~ 5g/L,
Reducing agent used in the preparation method of above-mentioned catalyst with core-casing structure is: a kind of in hydrazine hydrate, lithium triethylborohydride and sodium borohydride, the pH value of its solution is with 1 molL
-1naOH solution is adjusted to 13.
Direct borohydride fuel cell nucleocapsid structure anode catalyst of the present invention, adopt direct sodium borohydride-hydrogen peroxide fuel battery system to carry out anode catalyst performance evaluation.Nucleocapsid structure M
core-Au
shellthe preparation process of/C anode is: the M prepared with the present invention
core-Au
shellin mass ratio for the ratio of 1:4 takes 0.1g, add the 2mL deionized water with the XC-72 carbon dust, 3.5mL absolute ethyl alcohol and 20% PTFE 0.150g, ultrasonic agitation becomes the prepared Chinese ink shape after 30 minutes, with spraying method, catalyst prepared Chinese ink evenly is coated in to 1 * 1cm
2nickel screen on, the carrying capacity of controlling metal is 4mg/cm
2, then naturally dry, finally the nickel screen that scribbles catalyst 60
ounder C, 5MPa, hot pressing is 2 minutes, makes M
core-Au
shell/ C anode.The platinum guaze that negative electrode is 1 * 1cm (100 order), reference electrode is saturated Hg/Hg
2cl
2electrode (232 type).The cathode chamber of electro-chemical test groove and anode chamber's size are 3 * 4 * 5cm, with the NRE-212 cationic membrane, catholyte and anolyte are separated, and the exposed area of film is 1.0cm
2.The upper end, anode chamber has a blast pipe to be connected with U-shaped gas gauge, collects the volume that produces hydrogen under different current densities with drainage.The polarization experiment anolyte is 2mol/LNaOH+1 molL
-1naBH
4, catholyte is 2.0 molL
-1hCl+4.5 molL
-1h
2o
2.Adopt U.S. Princeton VMP III potentiostat to measure the performance of monocell.
The made catalyst with core-casing structure of the present invention demonstrates good BH in direct borohydride fuel cell monocell system
4 -the anodic oxidation performance.
For direct borohydride fuel cell nucleocapsid structure anode catalyst compared with prior art, the present invention's direct borohydride fuel cell nucleocapsid structure anode catalyst used is to BH in the present invention
4 -the activity of oxidation is high, and liberation of hydrogen is few, can effectively improve the utilization rate of fuel.
The accompanying drawing explanation
Fig. 1 is the Cu of the embodiment of the present invention 1 preparation
core-Au
shellthe transmission electron microscope of core-shell structure nanometer particle catalyst (TEM) photo;
In figure: particle diameter is 30nm, and middle black part is divided into Cu core nano particle, and outer light cloud form is partly the Au shell, and the thickness of shell is 6 nm approximately;
Fig. 2 is the battery performance curve that different catalysts is anode;
In figure: 1 is Cu prepared by the embodiment of the present invention 1
core-Au
shellthe core-shell structure nanometer particle catalyst;
2 is Cu, Au atomic molar than being the Cu-Au alloy catalyst of 1:1; 3 is the Au catalyst.
The specific embodiment
Below by embodiment, the specific embodiment of the present invention is described
Embodiment 1
(1) preparation of Cu nano particle: by Cu (NO
3) 3H
2o and polyethylene arsenic pyrrolidone (PVP) add in 20 ml ethylene glycol successively, and making the concentration of Cu atom in ethylene glycol is 20 mmol/L, and the concentration of polyethylene arsenic pyrrolidone (PVP) in ethylene glycol is 3 g/L.Stirring logical nitrogen 25 min fully mix it, then are heated to 60 ℃, continue to pass into nitrogen and constantly stir, and dripping concentration is 0.3 molL
-1hydrazine hydrate solution, the mole that adds hydrazine hydrate is 2 times of Cu element, rate of addition is 40 min
-1, react 40 min, prepare Cu nanocatalyst colloidal sol, then suction filtration, with the distilled water washing, obtain the Cu nano particle;
(2) the Cu nano particle in above-mentioned (1) is dissolved in 20 ml ethylene glycol again, add polyethylene arsenic pyrrolidone (PVP) under stirring, making its concentration is 3 g/L, pass into nitrogen and stir 30 minutes, add for the ratio of 1:1 the tetrahydrofuran solution that concentration is the 0.3g/L gold chloride according to Cu, Au atomic molar ratio again, constantly stir at 60 ℃ of temperature and continue to pass into nitrogen, then with 20 min
-1speed to drip concentration be 0.1 molL
-1hydrazine hydrate solution, the mol ratio of hydrazine hydrate and gold atom is 2.5:1, continue stirring reaction 2h at 60 ℃ of temperature, make nanocatalyst colloidal sol, then centrifugation, with the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours, 300 ℃ of heat treatment 2h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Cu-Au core-shell structure nanometer particle catalyst, as shown in Figure 1, observe nucleocapsid structure Cu-Au average particle diameter by Fig. 1 is 30nm to its TEM photo.
Take the gained eelctro-catalyst as anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.92V, by the peak use rate of the amounts of hydrogen computing fuel recorded, is 94%, and maximum power density is 124 mW/cm
2, its performance is as shown in curve in Fig. 21.For effect more of the present invention, in order to the standby Cu-Au alloy catalyst of below legal system or Au catalyst: polyethylene arsenic pyrrolidone (PVP) is added in 20 ml ethylene glycol, making its concentration is 3 g/L, pass into nitrogen and stir 30 minutes, then the ratio that is 1:1 according to Cu, Au mol ratio adds Cu (NO
3) 3H
2the tetrahydrofuran solution that O and concentration are the 0.3g/L gold chloride constantly stirs and continues to pass into nitrogen, then with 20 min at 60 ℃ of temperature
-1speed to drip concentration be 0.1 molL
-1hydrazine hydrate solution, the mol ratio of hydrazine hydrate and gold atom is 4.5:1, continue stirring reaction 2h at 60 ℃ of temperature, make Nanoalloy Cu-Au catalyst colloidal sol, then centrifugation, by the alternately washing of distilled water, ethanol, 50 ℃ of dryings of vacuum 18 hours, 300 ℃ of heat treatment 2h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Cu-Au alloy nano particle catalyst.The preparation method of Au nano-particle catalyst is the same with the Cu-Au alloy catalyst, only adds the tetrahydrofuran solution of gold chloride in preparation process.The gained eelctro-catalyst Cu-Au alloy of take is anode catalyst, at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is respectively as 1.34V, peak use rate by the amounts of hydrogen computing fuel recorded is 63%, and maximum power density is 62 mW/cm
2, its performance is as shown in curve in Fig. 22.The gained eelctro-catalyst Au of take is anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is respectively 1.18V, by the peak use rate of the amounts of hydrogen computing fuel recorded, is 88%, and maximum power density is 29 mW/cm
2, its performance is as shown in curve in Fig. 23.Known, the DBFC performance that the nucleocapsid structure Cu-Au nanocatalyst of take is anode is better than, with the Cu-Au alloy catalyst formed, also being better than independent Au catalyst.
Embodiment 2
(1) preparation of Ni nano particle: by NiCl
26H
2o and four octyl group ammonium bromides add in 20ml water successively, and making the concentration of Ni atom in water is 10 mmol/L, and the concentration of four octyl group ammonium bromides in water is 1.5 g/L.Stirring logical nitrogen fully mix it in 20 minutes, then are heated to 50 ℃, continue to pass into nitrogen and constantly stir, and dripping concentration is 0.3 molL
-1lithium triethylborohydride solution, adding the lithium triethylborohydride mole is 1.5 times of Ni element, rate of addition is 40 min
-1, react 40 min, prepare Ni nanocatalyst colloidal sol, then suction filtration, with the distilled water washing, obtain the Ni nano particle;
(2) the M nano particle in above-mentioned (1) is dissolved in 20 ml water again, add four octyl group ammonium bromides under stirring, the concentration of four octyl group ammonium bromides is 1.5g/L, pass into nitrogen and stir 30 minutes, add for the ratio of 0.5:1 the tetrahydrofuran solution that concentration is the 0.3g/L gold chloride according to Ni, Au atomic molar ratio again, constantly stir at 70 ℃ of temperature and continue to pass into nitrogen, then with 30 min
-1speed to drip concentration be 0.1 molL
-1lithium triethylborohydride solution, the mol ratio of lithium triethylborohydride and gold atom is 2.5:1, continue stirring reaction 2h at 70 ℃ of temperature, make nanocatalyst colloidal sol, then centrifugation, by the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours, 400 ℃ of heat treatment 1h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Ni-Au core-shell structure nanometer particle catalyst.By tem observation nucleocapsid structure Ni-Au average particle diameter, be 40nm.
Take the gained eelctro-catalyst as anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.85V, by the peak use rate of the amounts of hydrogen computing fuel recorded, is 95%, and maximum power density is 116mW/cm
2.
Embodiment 3
(1) prepare the Pt nano particle: by H
2ptCl
66H
2o and polyethylene glycol add in the 20ml oxolane successively, and making the concentration of Pt atom in oxolane is 30 mmol/L, and the concentration of polyethylene glycol in oxolane is 5 g/L.Stirring logical nitrogen fully mix it in 30 minutes, then are heated to 80 ℃, continue to pass into nitrogen and constantly stir, and dripping concentration is 0.3 molL
-1sodium borohydride solution, adding the sodium borohydride mole is 2.5 times of Pt element, rate of addition is 40 min
-1, react 60 min, prepare Pt nanocatalyst colloidal sol, then suction filtration, with the distilled water washing, obtain the Pt nano particle;
(2) the Pt nano particle in above-mentioned (1) is dissolved in the 20ml oxolane again, add polyethylene glycol under stirring, the concentration of polyethylene glycol is 5g/L, pass into nitrogen and stir 30 minutes, add for the ratio of 2.0:1 the tetrahydrofuran solution that concentration is the 0.3g/L gold chloride according to Pt, Au atomic molar ratio again, constantly stir at 70 ℃ of temperature and continue to pass into nitrogen, then with 20 min
-1speed to drip concentration be 0.1 molL
-1sodium borohydride solution, the mol ratio of sodium borohydride and gold atom is 2.5:1, continue stirring reaction 2h at 70 ℃ of temperature, make nanocatalyst colloidal sol, then centrifugation, by the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours, 350 ℃ of heat treatment 3h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Pt-Au core-shell structure nanometer particle catalyst.By tem observation nucleocapsid structure Pt-Au average particle diameter, be 20nm.
Take the gained eelctro-catalyst as anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.90V, by the peak use rate of the amounts of hydrogen computing fuel recorded, is 97%, and maximum power density is 126 mW/cm
2.
Embodiment 4
(1) prepare the Co nano particle: by CoCl
26H
2o and polyvinyl alcohol add in the 20ml isopropyl alcohol successively, and making the concentration of Co atom in isopropyl alcohol is 20 mmol/L, and the concentration of polyvinyl alcohol in isopropyl alcohol is 0.5 g/L.Stirring logical nitrogen fully mix it in 20 minutes, then are heated to 50 ℃, continue to pass into nitrogen and constantly stir, and dripping concentration is 0.3 molL
-1hydrazine hydrate solution, adding the hydrazine hydrate mole is 1.2 times of Co element, rate of addition is 40 min
-1, react 20 min, prepare M nanocatalyst colloidal sol, then suction filtration, with the distilled water washing, obtain the Co nano particle;
(2) the Co nano particle in above-mentioned (1) is dissolved in the 20ml isopropyl alcohol again, add polyvinyl alcohol under stirring, the concentration of polyvinyl alcohol is 0.5/L, pass into nitrogen and stir 30 minutes, add for the ratio of 1.5:1 the tetrahydrofuran solution that concentration is the 0.3g/L gold chloride according to Co, Au atomic molar ratio again, constantly stir at 65 ℃ of temperature and continue to pass into nitrogen, then with 25 min
-1speed to drip concentration be 0.1 molL
-1hydrazine hydrate solution, the mol ratio of hydrazine hydrate and gold atom is 2.5:1, continue stirring reaction 2h at 65 ℃ of temperature, make nanocatalyst colloidal sol, then centrifugation, by the alternately washing of distilled water, absolute ethyl alcohol alcohol, 50 ℃ of dryings of vacuum 18 hours, 300 ℃ of heat treatment 1.5 h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Co-Au core-shell structure nanometer particle catalyst.By tem observation nucleocapsid structure Co-Au average particle diameter, be 50 nm.
Take the gained eelctro-catalyst as anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.83V, by the peak use rate of the amounts of hydrogen computing fuel recorded, is 93%, and maximum power density is 108 mW/cm
2.
(1) preparation of Pd nano particle: by PdCl
22H
2o and polyethylene arsenic pyrrolidone (PVP) add in 20ml ethanol successively, and making the concentration of Pd atom in ethanol is 5 mmol/L, and the concentration of polyvinyl alcohol in ethanol is 1 g/L.Stirring logical nitrogen fully mix it in 30 minutes, then are heated to 60 ℃, continue to pass into nitrogen and constantly stir, and dripping concentration is 0.3 molL
-1sodium borohydride solution, adding the sodium borohydride mole is 2.5 times of Pd element, rate of addition is 40 min
-1, react 30 min, prepare Pd nanocatalyst colloidal sol, then suction filtration, with the distilled water washing, obtain the Pd nano particle;
(2) the Pd nano particle in above-mentioned (1) is dissolved in 20ml ethanol again, add four octyl group ammonium bromides under stirring, the concentration of four octyl group ammonium bromides is 4g/L, pass into nitrogen and stir 30 minutes, add for the ratio of 0.5:1 the tetrahydrofuran solution that concentration is the 0.3g/L gold chloride according to Pd, Au atomic molar ratio again, constantly stir at 60 ℃ of temperature and continue to pass into nitrogen, then with 20 min
-1speed to drip concentration be 0.1 molL
-1lithium triethylborohydride solution, the mol ratio of lithium triethylborohydride and gold atom is 2.5:1, continue stirring reaction 2h at 60 ℃ of temperature, make nanocatalyst colloidal sol, then centrifugation, by the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours, 400 ℃ of heat treatment 1h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Pd-Au core-shell structure nanometer particle catalyst.By tem observation nucleocapsid structure Pd-Au average particle diameter, be 10nm.
Take the gained eelctro-catalyst as anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.87V, by the peak use rate of the amounts of hydrogen computing fuel recorded, is 96%, and maximum power density is 113 mW/cm
2.
Embodiment 6
(1) preparation of Pd nanometer: by Pd (NO
3)
22H
2o and four octyl group ammonium bromides add in 20ml ethylene glycol successively, and making the concentration of Pd atom in ethylene glycol is 5 mmol/L, and the concentration of polyvinyl alcohol in ethylene glycol is 2 g/L.Stirring logical nitrogen fully mix it in 30 minutes, then are heated to 50 ℃, continue to pass into nitrogen and constantly stir, and dripping concentration is 0.3 molL
-1hydrazine hydrate solution, adding the hydrazine hydrate mole is 1.8 times of Pd element, rate of addition is 40 min
-1, react 50 min, prepare Pd nanocatalyst colloidal sol, then suction filtration, with the distilled water washing, obtain the Pd nano particle;
(2) the Pd nano particle in above-mentioned (1) is dissolved in 20ml ethylene glycol again, add polyethylene arsenic pyrrolidone (PVP) under stirring, its concentration is 2g/L, pass into nitrogen and stir 30 minutes, add for the ratio of 1:1 the tetrahydrofuran solution that concentration is the 0.3g/L gold chloride according to Pd, Au atomic molar ratio again, constantly stir at 60 ℃ of temperature and continue to pass into nitrogen, then with 20 min
-1speed to drip concentration be 0.1 molL
-1hydrazine hydrate solution, the mol ratio of hydrazine hydrate and gold atom is 2.5:1, continue stirring reaction 2h at 60 ℃ of temperature, make nanocatalyst colloidal sol, then centrifugation, by the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours, 300 ℃ of heat treatment 2h in the tube furnace argon gas atmosphere, grinding can obtain Powdered Pd-Au core-shell structure nanometer particle catalyst.By tem observation nucleocapsid structure Pd-Au average particle diameter, be 30 nm.
Take the gained eelctro-catalyst as anode catalyst, and at room temperature directly the open-circuit voltage of sodium borohydride-hydrogen peroxide fuel battery monocell is 1.86V, by the peak use rate of the amounts of hydrogen computing fuel recorded, is 97%, and maximum power density is 114 mW/cm
2.
Claims (4)
1. a direct borohydride fuel cell nucleocapsid structure anode catalyst, described catalyst is to be the nucleocapsid structure M that M, shell are Au by kernel
core-Au
shellnano-complex particle, the particle diameter 10 ~ 50nm of core-shell particles; Described M is Ni, Co, Cu or Pd; Described catalyst obtains by following method:
(1) prepare the M particle: M-salt and stabilizing agent are added in 20 mL solvents successively, making the concentration that the M-salinity is 5 ~ 30mmol/L and stabilizing agent is 0.5 ~ 5g/L, stirring and pass into nitrogen mixes it in 20 ~ 30 minutes, then be heated to 50 ~ 80 ℃, continue to pass into nitrogen and constantly stir, rear dropping concentration is 0.3 molL
-1reducing agent, the pH value of its reductant solution is with 1 molL
-1naOH solution is adjusted to 13, and adding the reducing agent mole is 1.2 ~ 2.5 times of M element, and rate of addition is 40 min
-1, react 20 ~ 60 min, make M nanocatalyst colloidal sol, then suction filtration, wash, and obtains the M nano particle;
(2) by the M nano particle in above-mentioned steps (1), again be dissolved in solvent, add the stabilizing agent that concentration is 0.5 ~ 5g/L under stirring, pass into nitrogen and stir 30 minutes, the ratio that is 0.5 ~ 2.0:1 in M, Au atomic molar ratio again adds the tetrahydrofuran solution that concentration is the 0.3g/L gold chloride, stir at 60 ~ 70 ℃ of temperature and continue to pass into nitrogen, then with 20 ~ 30 min
-1speed to drip concentration be 0.1 molL
-1reducing agent, the pH value of its reductant solution is with 1 molL
-1naOH solution is adjusted to 13, the mol ratio of reducing agent and gold atom is 2.5:1, continue stirring reaction 2h at 60 ~ 70 ℃ of temperature, make nanocatalyst colloidal sol, then centrifugation, by the alternately washing of distilled water, absolute ethyl alcohol, 50 ℃ of dryings of vacuum 18 hours, 300 ~ 400 ℃ of heat treatment 1 ~ 3h in the tube furnace argon gas atmosphere, grinding can obtain direct borohydride fuel cell nucleocapsid structure anode catalyst.
2. the method for claim 1, described solvent is a kind of in ethylene glycol, water, oxolane, isopropyl alcohol and ethanol.
3. the method for claim 1, described stabilizing agent is a kind of in polyvinylpyrrolidone (PVP), four octyl group ammonium bromides, polyethylene glycol and polyvinyl alcohol.
4. the method for claim 1, described reducing agent is a kind of in hydrazine hydrate, lithium triethylborohydride and sodium borohydride.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011102847589A CN102380400B (en) | 2011-09-23 | 2011-09-23 | Core-shell structural anode catalyst for direct borohydride fuel cells and preparation method thereof |
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| KR101926866B1 (en) * | 2012-07-17 | 2018-12-07 | 현대자동차주식회사 | Method for manufacturing palladium-platinium core-shell catalysts for fuel cells |
| CN104218249B (en) * | 2014-08-15 | 2016-04-06 | 太原理工大学 | For the preparation method of direct borohydride fuel cell anode catalyst with core-casing structure |
| CN105355935B (en) * | 2015-11-11 | 2018-04-10 | 大连理工大学 | A kind of preparation method and application of noble metal electrocatalyst |
| CN105536814B (en) * | 2015-12-08 | 2018-07-27 | 北京有色金属研究总院 | A kind of preparation method of catalyst with core-casing structure |
| CN106910907B (en) * | 2017-04-14 | 2021-02-23 | 中国科学院深圳先进技术研究院 | Core-shell structure catalyst, preparation method and application thereof |
| CN109935847A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of preparation method of the loaded platinum base alloy catalyst of low-temperature fuel cell |
| CN109309236B (en) * | 2018-10-26 | 2021-04-02 | 北方民族大学 | Anode catalytic material for direct borohydride fuel cell, anode material, preparation method of anode material and fuel cell |
| CN110911700B (en) * | 2019-11-21 | 2020-12-04 | 深圳氢时代新能源科技有限公司 | Catalyst, preparation method and application thereof |
| CN114635156B (en) * | 2022-03-01 | 2024-04-19 | 厦门大学 | Preparation method and application of Au@CuPd core-shell structure nano material |
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| CN101013752A (en) * | 2007-02-06 | 2007-08-08 | 太原理工大学 | Method for using three-dimensional electrode as direct anode of hydroboron fuel cell |
| CN101379639A (en) * | 2005-08-01 | 2009-03-04 | 布鲁克哈文科学协会 | Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof |
| CN101656313A (en) * | 2009-09-11 | 2010-02-24 | 太原理工大学 | Preparation method of catalyst for cathode of direct methanol fuel cell |
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| CN101379639A (en) * | 2005-08-01 | 2009-03-04 | 布鲁克哈文科学协会 | Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof |
| CN101013752A (en) * | 2007-02-06 | 2007-08-08 | 太原理工大学 | Method for using three-dimensional electrode as direct anode of hydroboron fuel cell |
| CN101656313A (en) * | 2009-09-11 | 2010-02-24 | 太原理工大学 | Preparation method of catalyst for cathode of direct methanol fuel cell |
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