CN102104157A - Preparation method for carbon dry gel - Google Patents
Preparation method for carbon dry gel Download PDFInfo
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- CN102104157A CN102104157A CN2009102484751A CN200910248475A CN102104157A CN 102104157 A CN102104157 A CN 102104157A CN 2009102484751 A CN2009102484751 A CN 2009102484751A CN 200910248475 A CN200910248475 A CN 200910248475A CN 102104157 A CN102104157 A CN 102104157A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a carbon carrier of a proton exchange membrane fuel cell, in particular to a preparation method for carbon dry gel. The carbon dry gel is prepared by m-dihydroxybenzene, formaldehyde and a metal salt serving as raw materials, wherein the metal salt comprises a soluble nitrate, a carbonate, a sulfate, an acetate or a halide of one or more metal elements in an IVB group, a VB group, a VIB group, a VIIB group, a VIII group, an IB group and an IIB group; the m-dihydroxybenzene serving as a precursor and the formaldehyde are in the mol ratio of 2:1; the m-dihydroxybenzene and the metal salt are in the mol ratio of 10:1-500:1; and a high-stability carbon carrier is prepared by graphitizing mixed organic carbon dry gel at the high temperature of 1,500 to 3,500 DEG C. When serving as an anti-corrosion carbon material and being used as a cathode catalyst carrier of the proton exchange membrane fuel cell, the carbon dry gel has high anti-corrosion performance and high stability in an acidic and high-potential environment of cell operation.
Description
Technical field
The present invention relates to the Proton Exchange Membrane Fuel Cells carbon carrier, specifically a kind of preparation method of corrosion-resistant, high stability as the charcoal xerogel of fuel battery cathode with proton exchange film catalyst carrier, described charcoal xerogel can be used as carrier, is used for the fuel battery cathode with proton exchange film catalyst.
Background technology
Fuel cell is a kind of conversion equipment that directly chemical energy of material is converted into electric energy, is considered to the 4th class generation technology behind hydroelectric power generation, thermal power generation and nuclear energy power generation.With hot machine form work, the chemical energy of the most of fuel in the fuel cell can directly not be converted to electric energy to fuel cell, and power generation process is not subjected to the restriction of Carnot cycle, has higher energy conversion efficiency (40～60%).Simultaneously, produce SO2, NO hardly in the fuel cell power generation process
xWith harmful substances such as suspended matters, do not emit greenhouse gas CO2 yet, be a kind of generation mode that meets the cleaning of current social enviroment protection theory.Wherein particularly outstanding is hydrogen-oxygen proton exchange membrane fuel cell, and its product has only water.Whole fuel cell is to be in series by single battery in the application, the power of fuel cell can by several watts to MW class, can use to extensive generating from mobile phone.Simultaneously, the required auxiliary equipment of fuel cell is few, and a large amount of power transmission lines have been saved in the use of almost can generating electricity anywhere, and convenient and reliable operation, flexibility are big.These advantages make fuel cell be acknowledged as the cleaning of 21 century first-selection, generation technology efficiently, are subjected to the great attention of national governments and enterprise in recent years.
At present, the stability of PEMFC long-time running and expensive price are its bottlenecks of realizing the commercialization maximum, and in order further to improve the performance of PEMFC and to reduce cost, research work mainly concentrates on the improvement of eelctro-catalyst and polymer dielectric film.Material with carbon element is as the carrier of catalyst and the skeleton of porous gas diffusive electrode, and its physics and surface chemical property directly influence the performance of catalyst and entire cell.In the PEMFC operational environment, particularly under high current density, when supply of fuel is deficient and after the PEMFC long-time running, the oxide etch phenomenon of carbon carrier is serious, oxidizing process can be by C+2H
2O=CO
2+ 4H
++ 4e
-(E=0.207V vs.RHE) and C+H
2O → H
2+ CO (when having Pt) expression.The corrosion of the interior carbon of battery directly causes supporting in its surperficial catalyst activity component runs off, reunites, and the metallic catalyst particle diameter increases, and active area reduces, and whole catalyst layer structure is damaged; Simultaneously, the oxide etch of material with carbon element also can influence its surperficial hydrophilicity and hydrophobicity, makes the transmission duct of reactant and product stop up.Above phenomenon finally causes battery performance decline, the useful life of PEMFC to shorten.As seen, improve the antioxidant anticorrosive performance of carbon support material, develop the corrosion-resistant material with carbon element and the non-material with carbon element carrier of novel stabilising, significant for the stability and the useful life of improving the PEMFC long-time running.
In recent years, many new carbon such as carbon nano-tube, carbon nano-fiber, nano cages, charcoal gel cell catalyst carriers that act as a fuel that are similar to are applied in the fuel cell, make the antioxidant anticorrosive performance of catalyst carrier that improvement to a certain degree arranged, but performances such as pore structure, specific area remain further to be optimized.Wherein, the charcoal gel rubber material has higher electric conductivity, bigger mesopore ratio, suitable characteristics such as specific area, makes it be suitable as very much fuel-cell catalyst carrier.Simultaneously, studies show that metal-doped material can obtain the degree of graphitization higher than raw material in the same high temperature heat treatment process, reduced the preparation cost of graphitized carbon material.
Metal-doped high temperature graphitization carbon gel rubber material has good stable and corrosion resistance, and this has determined that it can stable existence under the high potential of Proton Exchange Membrane Fuel Cells and acid condition.Metal-doped high temperature graphitization carbon gel rubber material has bigger specific area, suitable catalyst-loaded central hole structure and favorable conductive heat conductivility.Simultaneously, the interpolation of slaine has not only improved the degree of graphitization of high-temperature process material with carbon element, and part is doped in the metal of graphite-structure and the active component acting in conjunction that is supported, the activity of raising PEM fuel-cell catalyst and the stability of long-time running.Therefore, when improving metal-doped high temperature graphitization carbon carrier stability, further increase the synergy of carrier and active component, improve the catalytic activity of hydrogen reduction, can improve the performance of Proton Exchange Membrane Fuel Cells and the stability of long-time running widely, break through the bottleneck of Proton Exchange Membrane Fuel Cells commercial applications.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of charcoal xerogel, described charcoal xerogel can be used as carrier, is used for the fuel battery cathode with proton exchange film catalyst; Prepared charcoal xerogel has bigger specific area, suitable catalyst-loaded central hole structure and favorable conductive heat conductivility, be applied in the fuel battery cathode with proton exchange film catalyst long-time running corrosion resistance good stability, the active height of oxygen reduction reaction.
For achieving the above object, the technical solution used in the present invention is:
A kind of preparation method of the charcoal xerogel as the fuel battery cathode with proton exchange film catalyst carrier, described charcoal xerogel is a raw material with resorcinol, formaldehyde and slaine, adopts following process to prepare:
(1) with resorcinol and the solvent ratio in 0.1～10ml solvent/1g resorcinol, mixed dissolution is even, obtains clear solution A;
(2) slaine is joined in the above-mentioned solution A, mix, obtain solution B, wherein the mol ratio of metallic atom is 10: 1～1500: 1 in resorcinol and the slaine;
(3) in resorcinol and 1: 1～4: 1 ratio of formaldehyde mole ratio, dripping concentration in the solution B in stirring is 20-40wt% formalin, mixes, and continues to stir until reaction at 20～100 ℃ to form gel C;
(4) gel C is transferred to vacuum drying chamber 60～100 ℃ of following vacuumize burin-in process 3～12 days, takes out the back and pulverize and grind, obtain pressed powder D;
(5) with pressed powder D at inert atmosphere (as: N
2, Ar etc.) in 1600～3500 ℃ of high temperature graphitizations handled 1～10 hour, inert blowing gas is swept to room temperature; Adopt 0.5～5M acid solution eccysis unreacted metal salt, promptly get charcoal xerogel of the present invention after the drying.
Described slaine is the soluble-salt of one or more transition metals in IVB, VB, VIB, VIIB, VIII, IB and the IIB family; Described soluble-salt is nitrate, carbonate, sulfate, acetate, halide, dinitroso two amine salt, acetylacetonate or encircles in complex compound porphyrin, the phthalein mountain valley with clumps of trees and bamboo and the polymer thereof one or more greatly.
Described transition metal is preferably one or more among Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, the W.
The mol ratio of described resorcinol and formaldehyde is preferably 2: 1, and the mol ratio of resorcinol and slaine is preferably 10: 1～and 500: 1; The graphitization processing temperature of metal organogel is preferably 1600～2800 ℃.
Described acid is nitric acid, hydrochloric acid or sulfuric acid; The mass concentration of described formalin is generally 30～40%; Mass concentration is preferably 37～40%;
Described solvent is one or more in water, ethanol, isopropyl alcohol, the ethylene glycol;
When solvent is a kind of in water, ethanol, isopropyl alcohol, the ethylene glycol, wherein step 3) is 20～80 ℃ for aqueous solvent stirring environment, it is 20～78 ℃ that alcohol solvent stirs environment, and it is 20～82 ℃ that isopropanol solvent stirs environment, and it is 60～100 ℃ that ethylene glycol solvent stirs environment; Ethanol and isopropyl alcohol have dispersed preferably, and product is uniformly dispersed, and ethylene glycol is applicable to higher temperature environment.
When solvent is a kind of in water, ethanol, the isopropyl alcohol; Step 3) stirs environment and is preferably 20-50 ℃ of environmental condition gentleness, reduces the solvent evaporates amount, can obtain the gel rubber material of suitable specific area;
Advantage of the present invention is:
1. effect is good.When the charcoal xerogel was used on fuel battery cathode with proton exchange film, it was active and stable for a long time to show higher oxygen reduction reaction.
2. cost of material of the present invention is lower, and technological process is simple, the cycle is short, precursor component charing black leadization simultaneously once can be able to be prepared high-specific surface area, the carbon carrier of high stability; In addition, slaine mixes and has relaxed the process conditions of graphitization processing; Simultaneously, the solvent safety that uses in the charcoal xerogel preparation process, nontoxic, environmentally safe.
3. charcoal xerogel of the present invention is in the gel forming process, and adding, adjusting precursor solution concentration and reaction environment temperature by controlling different amount slaines can prepare the adjustable charcoal xerogel material of pore structure and controllable specific surface area.
4. charcoal xerogel of the present invention has higher degree of graphitization after high temperature graphitization is handled, stability is higher than common carrier, has suitable pore structure and specific area simultaneously.
5. charcoal xerogel of the present invention has improved charcoal xerogel configuration of surface by doped metallic elements, has strengthened the adhesion between catalytic active component and carrier, has increased the stability of catalyst.
6. have wide range of applications.As a kind of stable carbon carrier, the active component that the charcoal gel rubber material of high graphitization can support is one or more in precious metals pt, Pt alloy, non-Pt metal and the nonmetallic materials.Be significant for catalytic activity that improves non-precious metal catalyst and commercialization process stable, that accelerate Proton Exchange Membrane Fuel Cells.
In a word, the present invention has prepared high stability charcoal xerogel material by the process of high temperature graphitization, and this material with carbon element has advantages of higher stability and hydrogen reduction (ORR) activity when supporting active component as catalyst of fuel batter with proton exchange film; The precursor price of material with carbon element is low; Simultaneously, this carbon support material preparation process is simple, applied range, can be used as the catalyst carrier of different activities component, environmentally safe.
Description of drawings
Fig. 1 is the graph of pore diameter distribution of the Co-CX carrier of 1800 ℃ of graphitization processing of the present invention;
Fig. 2 is the transmission electron microscope photo of the Co-CX carrier of 1800 ℃ of graphitization processing of the present invention;
Fig. 3 is that 20% Pt/Co-CX catalyst is at 0.5M H for the Co-CX preparing carriers content of 1800 ℃ of graphitization processing of the present invention
2SO
4Quicken the hydrogen reduction polarization curve of decay front and back in the solution;
Fig. 4 is that 20% Pt/Co-CX catalyst is at 0.5M H for the Co-CX preparing carriers content of 1500 ℃ of graphitization processing of the present invention
2SO
4Quicken the hydrogen reduction polarization curve of decay front and back in the solution;
Fig. 5 is that 20% Pt/C catalyst is at 0.5M H for the commercialization loading
2SO
4Quicken the hydrogen reduction polarization curve of decay front and back in the solution;
Fig. 6 quickens battery performance curve before and after the decay for being 20% Pt/Co-CX with the content of 1800 ℃ of processing of the present invention as the Proton Exchange Membrane Fuel Cells of cathod catalyst; The working temperature of battery is 80 ℃, and as anode catalyst, anode and cathode pressure is H with Pt/C
2/ O
2=0.2/0.2MPa;
To be 20% Pt/C for the commercialization loading quicken performance curve before and after the decay as the Proton Exchange Membrane Fuel Cells of cathod catalyst to Fig. 7; The working temperature of battery is 80 ℃, and as anode catalyst, anode and cathode pressure is H with Pt/C
2/ O
2=0.2/0.2MPa;
To be 20% Pt/Co-CX for the content of 800 ℃ of processing of Comparative Examples quicken battery performance curve before and after the decay as the Proton Exchange Membrane Fuel Cells of cathod catalyst to Fig. 8; The working temperature of battery is 80 ℃, and as anode catalyst, anode and cathode pressure is H with Pt/C
2/ O
2=0.2/0.2MPa;
Fig. 9 is for the content of 1800 ℃ of processing of the present invention being 47.6% the Pt/Co-CX catalyst performance curve after as the Proton Exchange Membrane Fuel Cells decay of cathod catalyst; The working temperature of battery is 80 ℃, and as anode catalyst, Nafion212 is a proton exchange membrane with Pt/C, and anode and cathode pressure is H
2/ O
2=0.2/0.2Mpa, air inlet and humidification temperature are H
2/ O
2=90/85 ℃;
To be 47.6% Pt/C for the commercialization loading quicken performance curve before and after the decay as the Proton Exchange Membrane Fuel Cells of cathod catalyst to Figure 10; The working temperature of battery is 80 ℃, and as anode catalyst, Nafion212 is a proton exchange membrane with Pt/C, and anode and cathode pressure is H
2/ O
2=0.2/0.2MPa, air inlet and humidification temperature are H
2/ O
2=90/85 ℃.
Embodiment
Below by embodiment the present invention is described in detail, but the present invention is not limited only to embodiment.
The 6.16g resorcinol is dissolved in the 4mL deionized water, forms clear solution A; Be added drop-wise among the above-mentioned clear solution A during the cabaltous nitrate hexahydrate aqueous solution of getting 5.13ml concentration and be 20mg/mL stirs, mix, obtain solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 60 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 80 ℃ of following vacuumize burin-in process 7d, takes out the back and pulverize grinding, obtain pressed powder D; Pressed powder D 1800 ℃ of high temperature graphitizations in N2 are handled 3h, N
2Air-blowing is swept to room temperature, 0.5M H
2SO
4Solution eccysis slaine obtains 32: 1 charcoal xerogel support C o-CX of resorcinol and cobalt nitrate mol ratio.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 20% Pt/Co-CX1800 catalyst.
As can be seen from Figure 1, charcoal xerogel pore-size distribution concentrates on 3-4nm and 30-100nm.The aperture major part is between the mesopore scope, and specific area is big, meets fuel-cell catalyst and supports demand.
Contrast as can be seen from Fig. 6 and Fig. 7, quicken before and after the decay, supported carrier Pt catalyst cell performance of the present invention all is higher than the battery performance of JM company homology module amount commercial catalyst.Wherein, at 1000mA/cm
2The place, preparing carriers catalyst potential decay 39mV of the present invention, JM catalyst decay 63mV.Illustrate that this carrier has corrosion resistance and stability preferably in the fuel cell operation process.
Comparative Examples
The 6.16g resorcinol is dissolved in the 4mL deionized water, forms clear solution A; Be added drop-wise among the above-mentioned clear solution A during the cabaltous nitrate hexahydrate aqueous solution of getting 5.13ml concentration and be 20mg/mL stirs, mix, obtain solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 60 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 80 ℃ of following vacuumize burin-in process 7d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 800 ℃ of heat treatment 3h, N
2Air-blowing is swept to room temperature, 0.5M H
2SO
4Solution eccysis slaine obtains 32: 1 charcoal xerogel support C o-CX of resorcinol and cobalt nitrate mol ratio.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 20% Pt/Co-CX800 catalyst.
Battery quickens attenuation test as can be seen among Fig. 8, and the battery performance decay is serious, at 1000mA/cm
2The place, this preparing carriers catalyst potential decay 87mV.Experimental result shows, because treatment temperature does not reach the high graphitization depth, carrier is under the highly acid fuel cell operation environment of high potential, and less stable is partly corroded, and the catalyst-loaded loss of institute is reunited serious.So high temperature graphitization is handled the raising to the stable corrosion resistance of carrier, has important role.
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.4355g four hydration cobalt acetate solids and add among the above-mentioned clear solution A, mix and obtain solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 20 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 60 ℃ of following vacuumize burin-in process 3d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 1500 ℃ of high temperature graphitizations handle 1h, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains 32: 1 charcoal xerogel support C o-CX1500 of resorcinol and cobalt acetate mol ratio.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 20% Pt/Co-CX1500 catalyst.Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/Co-CX1500 catalyst cell performance all is higher than the battery performance of JM company homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 41mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
The 6.16g resorcinol is dissolved in the 2mL deionized water, forms clear solution A; Get in the stirring of 0.7063g nine nitric hydrate iron solids and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 90 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 80 ℃ of following vacuumize burin-in process 3d, takes out the back and pulverize grinding, obtain pressed powder D; Pressed powder D 1900 ℃ of high temperature graphitizations in Ar are handled 5h, and the Ar air-blowing is swept to room temperature, 4M HNO
3Solution eccysis slaine obtains 32: 1 charcoal xerogel carrier Fe-CX1900 of resorcinol and ferric nitrate mol ratio.Being equipped with mass fraction by the sodium borohydride reduction legal system is 20% Pt/Fe-CX1900 catalyst.Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/Fe-CX1900 catalyst cell performance all is higher than the battery performance of JM company homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 32mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in the stirring of 0.4355g four hydration cobalt acetate solids and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 40 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 90 ℃ of following vacuumize burin-in process 10d, takes out the back and pulverize grinding, obtain pressed powder D; Pressed powder D 1800 ℃ of high temperature graphitizations in Ar are handled 8h, and the Ar air-blowing is swept to room temperature, and 3M HCl solution eccysis slaine obtains 32: 1 charcoal xerogel support C o-CX1800 of resorcinol and cobalt acetate mol ratio.Being equipped with mass fraction by the sodium borohydride reduction legal system is 47.6% Pt/Co-CX1800 catalyst.
Contrast as can be seen from Fig. 9 and Figure 10, quicken before and after the decay, the battery performance of supported carrier Pt catalyst of the present invention all is higher than the battery performance of the commercial catalyst of TKK company homology module amount.Wherein, at 1000mA/cm
2The place, preparing carriers catalyst potential decay 31mV of the present invention, TKK catalyst decay 47mV.Illustrate that this carrier has corrosion resistance and stability preferably in the fuel cell operation process.
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 1.6298g cobalt nitrate solid and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 40 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 70 ℃ of following vacuumize burin-in process 5d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 2200 ℃ of high temperature graphitizations handle 10h, N
2Air-blowing is swept to room temperature, and 1M HCl solution eccysis slaine obtains 10: 1 charcoal xerogel support C o-CX2200 of resorcinol and cobalt nitrate mol ratio.It by hydrogen reduction method preparation quality mark 10% Pt/Co-CX2200 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/Co-CX2200 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 28mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.1118g hydration Schweinfurt green solid and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 80 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 85 ℃ of following vacuumize burin-in process 7d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 2700 ℃ of high temperature graphitizations handle 10h, N
2Air-blowing is swept to room temperature, 0.5M H
2SO
4Solution eccysis slaine obtains 100: 1 charcoal xerogel support C u-CX2700 of resorcinol and Schweinfurt green mol ratio.It by hydrogen reduction method preparation quality mark 50% Pt/Cu-CX2700 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/Cu-CX2700 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 21mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
The 6.16g resorcinol is dissolved in the 20mL deionized water, forms clear solution A; Get in the stirring of 0.1662g Nickel dichloride hexahydrate solid and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 20 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 60 ℃ of following vacuumize burin-in process 12d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 2200 ℃ of high temperature graphitizations handle 3h, the N2 air-blowing is swept to room temperature, 5M HCl solution eccysis slaine obtains 80: 1 charcoal xerogel carrier Ni-CX2200 of resorcinol and nickel chloride mol ratio.Being equipped with mass fraction by the sodium borohydride reduction legal system is 5% PtCo/Ni-CX2200 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and PtCo/Ni-CX2200 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 24mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in the stirring of 0.0132g four hydration vanadic sulfate solids and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 40 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 90 ℃ of following vacuumize burin-in process 5d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 2800 ℃ of high temperature graphitizations handle 3h, N
2Air-blowing is swept to room temperature, and 2M HCl solution eccysis slaine obtains 1000: 1 charcoal xerogel carrier V-CX2800 of resorcinol and vanadic sulfate mol ratio.Being equipped with mass fraction by the sodium borohydride reduction legal system is 40% Pt/V-CX2800 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/V-CX2800 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 24mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 9
The 6.16g resorcinol is dissolved in the 5mL deionized water, forms clear solution A; Get in the stirring of 0.0555 zinc nitrate hexahydrate solid and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 30 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 65 ℃ of following vacuumize burin-in process 8d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 1500 ℃ of high temperature graphitizations handle 3h, N
2Air-blowing is swept to room temperature, 1M HNO
3Solution eccysis slaine obtains 300: 1 charcoal xerogel carrier Zn-CX1500 of resorcinol and zinc nitrate mol ratio.It by hydrogen reduction method preparation quality mark 20% Pt/Zn-CX1500 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/Zn-CX1500 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 27mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 10
The 6.16g resorcinol is dissolved in the 15mL deionized water, forms clear solution A; Get in the stirring of 0.4480g Chromium nitrate (Cr(NO3)3),nonahydrate solid and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 50 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 85 ℃ of following vacuumize burin-in process 6d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 2800 ℃ of high temperature graphitizations handle 5h, N
2Air-blowing is swept to room temperature, 0.5M HNO
3Solution eccysis slaine obtains 50: 1 charcoal xerogel support C r-CX2800 of resorcinol and chromic nitrate mol ratio.It by hydrogen reduction method preparation quality mark 20% Pt/Cr-CX2800 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/Cr-CX2800 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 34mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 11
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in the stirring of 0.0299g two nitric hydrate oxygen zirconium solids and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 30 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 85 ℃ of following vacuumize burin-in process 5d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 1600 ℃ of high temperature graphitizations handle 4h, N
2Air-blowing is swept to room temperature, 5M H
2SO
4Solution eccysis slaine obtains 500: 1 charcoal xerogel carrier Zr-CX1600 of resorcinol and zirconyl nitrate mol ratio.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 30% Pt/Zr-CX1600 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/Zr-CX1600 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 35mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 12
The 6.16g resorcinol is dissolved in the 5mL deionized water, forms clear solution A; Get in the stirring of 0.0107g two tungsten oxchloride solids and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 20 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 70 ℃ of following vacuumize burin-in process 7d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 2400 ℃ of high temperature graphitizations handle 3h, N
2Air-blowing is swept to room temperature, 1M HNO
3Solution eccysis slaine obtains 1500: 1 charcoal xerogel carrier W-CX2400 of resorcinol and two tungsten oxchloride mol ratios.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 30% Pt/W-CX2400 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/W-CX2400 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 25mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 13
The 6.16g resorcinol is dissolved in the 0.1mL deionized water, forms clear solution A; Get in the stirring of 0.0351g four nitric hydrate manganese solids and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 20 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 85 ℃ of following vacuumize burin-in process 5d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 2400 ℃ of high temperature graphitizations handle 5h, N
2Air-blowing is swept to room temperature, 1M H
2SO
4Solution eccysis slaine obtains 400: 1 charcoal xerogel carrier Mn-CX2400 of resorcinol and manganese nitrate mol ratio.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 30% Pt/Mn-CX2400 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/Mn-CX2400 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 18mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 14
The 6.16g resorcinol is dissolved in the 3mL deionized water, forms clear solution A; Get in the stirring of 0.1372g ammonium molybdate solid and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 20 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 80 ℃ of following vacuumize burin-in process 7d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 2500 ℃ of high temperature graphitizations handle 5h, N
2Air-blowing is swept to room temperature, 2M H
2SO
4Solution eccysis slaine obtains 80: 1 charcoal xerogel carrier Mo-CX2500 of resorcinol and ammonium molybdate mol ratio.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 10% Pt/Mo-CX2500 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/Mo-CX2500 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 16mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 15
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in the stirring of 0.2716g cabaltous nitrate hexahydrate and 0.3771g nine nitric hydrate iron solids and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 25 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 85 ℃ of following vacuumize burin-in process 6d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 1800 ℃ of high temperature graphitizations handle 3h, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains 60: 1: 1 charcoal xerogel support C oFe-CX1800 of resorcinol cobalt nitrate ferric nitrate mol ratio.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 50% Pt/CoFe-CX1800 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay, and Pt/CoFe-CX1800 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 29mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 16
The 6.16g resorcinol is dissolved in the 8mL deionized water, forms clear solution A; Get in the stirring of 0.1630g cabaltous nitrate hexahydrate and 0.2787g six hydration nickel acetate solids and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 25 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 85 ℃ of following vacuumize burin-in process 6d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 1800 ℃ of high temperature graphitizations handle 3h, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains 100: 1: 2 charcoal xerogel support C oNi of resorcinol cobalt nitrate nickel acetate mol ratio
2-CX1800.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 50% Pt/CoNi
2-CX1800 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay Pt/CoNi
2-CX1800 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 27mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 17
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in the stirring of 0.0465g four hydration cobalt acetates and 0.2029g Gerhardite solid and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 35 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 85 ℃ of following vacuumize burin-in process 8d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 1600 ℃ of high temperature graphitizations handle 3h, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains 200: 1: 3 charcoal xerogel support C oCu of resorcinol cobalt acetate copper nitrate mol ratio
3-CX1600.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 20% Pt/CoCu
3-CX1600 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay Pt/CoCu
3-CX1600 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 32mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 18
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.4525g nine nitric hydrate iron and 0.1628g Nickelous nitrate hexahydrate solid and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 25 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 95 ℃ of following vacuumize burin-in process 6d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 1700 ℃ of high temperature graphitizations handle 2h, N
2Air-blowing is swept to room temperature, 0.5M HNO
3Solution eccysis slaine obtains 100: 2: 1 charcoal xerogel carrier Fe of resorcinol ferric nitrate nickel nitrate mol ratio
2Ni-CX1700.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 10% Pt/Fe
2The Ni-CX1700 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay Pt/Fe
2Ni-CX1700 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 33mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 19
The 6.16g resorcinol is dissolved in the 10mL deionized water, forms clear solution A; Get in the stirring of 0.4525g nine nitric hydrate iron and 0.4490g two nitric hydrate oxygen zirconium solids and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 25 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 75 ℃ of following vacuumize burin-in process 6d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 2300 ℃ of high temperature graphitizations handle 1h, N
2Air-blowing is swept to room temperature, 0.5M HNO
3Solution eccysis slaine obtains 100: 2: 3 charcoal xerogel carrier Fe of resorcinol ferric nitrate zirconyl nitrate mol ratio
2Zr
3-CX2300.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 10% Pt/Fe
2Zr
3-CX2300 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay Pt/Fe
2Zr
3-CX2300 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 24mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Embodiment 20
The 6.16g resorcinol is dissolved in the 5mL deionized water, forms clear solution A; Get in the stirring of 0.2090g nine hydration nickel acetates and 0.0748g two nitric hydrate oxygen zirconium solids and add among the above-mentioned clear solution A, mixed dissolution evenly obtains solution B; Drip 9.08g formalin in the solution B in stirring, further mix, in 25 ℃ of environment, continue to stir, form gel C until reaction; Gel C is transferred to vacuum drying chamber at 95 ℃ of following vacuumize burin-in process 6d, takes out the back and pulverize grinding, obtain pressed powder D; With pressed powder D at N
2In 2700 ℃ of high temperature graphitizations handle 1h, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains 200: 3: 1 charcoal xerogel carrier Ni of resorcinol nickel acetate zirconyl nitrate mol ratio
3Zr
1-CX2700.Being equipped with mass fraction by the reduction of ethylene glycol legal system is 5% Pt/Ni
3Zr
1-CX2700 catalyst.
Electrochemistry and battery quicken the attenuation test result and show, quicken before and after the decay Pt/Ni
3Zr
1-CX2700 catalyst cell performance all is higher than the battery performance of homology module amount commercial catalyst.Wherein at 1000mA/cm
2Place's cell potential decays to 19mV, is lower than the commercialization catalyst.This shows that this catalyst has active and stable preferably.
Claims (8)
1. the preparation method of a charcoal xerogel is characterized in that:
Described charcoal xerogel is a raw material with resorcinol, formaldehyde and slaine, adopts following process to prepare:
(1) with resorcinol and the solvent ratio in 0.1～10ml solvent/1g resorcinol, mixed dissolution is even, obtains clear solution A;
(2) slaine is joined in the above-mentioned solution A, mix, obtain solution B, wherein the mol ratio of metallic atom is 10: 1～1500: 1 in resorcinol and the slaine;
(3) in resorcinol and 1: 1～4: 1 ratio of formaldehyde mole ratio, dripping concentration in the solution B in stirring is 20-40wt% formalin, mixes, and continues to stir until reaction at 20～100 ℃ to form gel C;
(4) gel C is transferred to vacuum drying chamber 60～100 ℃ of following vacuumize burin-in process 3～12 days, takes out the back and pulverize and grind, obtain pressed powder D;
(5) pressed powder D 1500～3500 ℃ of high temperature graphitizations in inert atmosphere were handled 1～10 hour, inert blowing gas is swept to room temperature; Adopt 0.5～5M acid solution eccysis unreacted metal salt, promptly get charcoal xerogel of the present invention after the drying.
2. it is characterized in that in accordance with the method for claim 1: described slaine is the soluble-salt of one or more transition metals in IVB, VB, VIB, VIIB, VIII, IB and the IIB family.
3. it is characterized in that in accordance with the method for claim 2: described soluble-salt is nitrate, carbonate, sulfate, acetate, halide, dinitroso two amine salt, acetylacetonate or encircles in complex compound porphyrin, the phthalein mountain valley with clumps of trees and bamboo and the polymer thereof one or more greatly.
4. it is characterized in that in accordance with the method for claim 2: described transition metal is one or more among Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, the W.
5. in accordance with the method for claim 1, it is characterized in that: the mol ratio of described resorcinol and formaldehyde is 2: 1, and the mol ratio of resorcinol and slaine is 10: 1～500: 1.
6. it is characterized in that in accordance with the method for claim 1: the graphitization processing temperature of metal organogel is 1500～2800 ℃.
7. it is characterized in that in accordance with the method for claim 1: described acid is nitric acid, hydrochloric acid or sulfuric acid; The mass concentration of described formalin is 30～40%.
8. it is characterized in that in accordance with the method for claim 1: described solvent is one or more in water, ethanol, isopropyl alcohol, the ethylene glycol;
When solvent is a kind of in water, ethanol, isopropyl alcohol, the ethylene glycol, wherein step 3) is 20～80 ℃ for aqueous solvent stirring environment, it is 20～78 ℃ that alcohol solvent stirs environment, and it is 20～82 ℃ that isopropanol solvent stirs environment, and it is 60～100 ℃ that ethylene glycol solvent stirs environment.
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| CN102856562A (en) * | 2011-06-30 | 2013-01-02 | 中国科学院大连化学物理研究所 | Carbon nanotube doped carbon gel catalyst for fuel cell and its application |
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