CN104289242A - Preparation method of carbon based catalyst with high graphitization degree and used for fuel cell cathode - Google Patents
Preparation method of carbon based catalyst with high graphitization degree and used for fuel cell cathode Download PDFInfo
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Abstract
The invention relates to a preparation method of a carbon based catalyst with high graphitization degree and used for a fuel cell cathode. The method is as below: using pitch as a carbon precursor, heating and melting the precursor by high temperature, and immersing the precursor in a template agent; mixing evenly, adding a nitrogen-containing precursor, and adding metal salt; then carrying out drying, high temperature treatment and two times of nitridation; then washing in an acidic solution and removing the template; and finally filtering, washing and drying to obtain the nitrogen doped carbon based catalyst material with high degree of graphitization. The catalyst has high graphitization degree, high specific surface area and ordered pore structure. The catalyst used as the cathode catalyst for a proton exchange membrane fuel cell shows good oxygen reduction activity, and the catalyst is environment-friendly, low in cost, microscopic controllable, and rich in resources, and is expected to become electric catalyst for proton exchange membrane fuel cells.
Description
Technical field
The present invention relates to fuel-cell catalyst preparation field, particularly a kind of preparation method of cathod catalyst.
Background technology
As the one of fuel cell, Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, PEMFC) with pure hydrogen or purification reformed gas for fuel, take perfluoro sulfonic acid membrane as electrolyte, can stable operation between room temperature is to 100 DEG C, thus have can room temperature start fast, discharge without electrolyte loss, contamination-free, specific power and specific energy high.In future will take hydrogen as the hydrogen energy era of main energetic carrier, and Proton Exchange Membrane Fuel Cells is as electric powered motor source, and the aspects such as portable power supply and dispersion power station have broad application prospects.
Eelctro-catalyst is one of critical material of Proton Exchange Membrane Fuel Cells (PEMFC), current fuel battery negative pole oxygen reduction catalyst mainly Pt/C catalyst; Anode mainly uses the PtRu/C catalyst of anti-CO.The cost that this kind of catalyst is too high is one of business-like key factor of restriction Proton Exchange Membrane Fuel Cells.The cathode reaction of PEMFC is oxygen reduction reaction, its electrode reaction speed far below the hydroxide reaction of anode, PEMFC loss in efficiency more than 80% from negative electrode.ORR is four complicated electron reactions, occurs multiple intermediate state species, as hydrogen peroxide, ADSORPTION STATE hydroxyl etc. in the reaction mechanism mechanism of reaction.In addition, along with environment worsens increasingly, air quality degradation, the catalyst poisoning problem that in air, impurity causes becomes one of key factor affecting its durability, is thus shown great attention in recent years.Therefore, the commercial development tool of ORR catalyst to PEMFC of development high activity, low cost, high mithridatism is of great significance.
Carbon nano-material has the features such as bigger serface, homogeneous nanostructured, strong corrosion resistant performance, high conductivity, is thus widely used in electronics, catalysis, storage hydrogen and electrochemical field.But Nano carbon itself has catalytic activity hardly to fuel cell oxygen reduction reaction.Research in recent years shows, the nano-carbon material of some doping N or B is in oxygen reduction reaction process, and show higher oxygen reduction reaction catalytic activity, this result has promoted rapidly the research and development of carbon-supported catalysts.
It is presoma with pitch that Chinese patent (application number 200310108845.4) provides a kind of, SiO
2for the preparation method of template high graphitization material with carbon element, prepared material with carbon element has high graphitization degree.But due to Carbon Materials prepared by the method, substantially not there is hydrogen reduction catalytic performance without N doping;
Chinese patent (application number 200910248475.1) provides a kind of preparation method utilizing phenolic resins to prepare N doping catalyst, due to resorcinol price, limits its industrialized production.In addition, adopt the Carbon Materials of this precursor power, need, higher than more than 2000 DEG C, could high graphitization be realized.But the high-temperature process of this more than 2000 DEG C, the hole of material can be caused to subside, cause specific area and pore volume sharply to decline.
The present invention is directed to above-mentioned shortcoming, the preparation method of the doping carbon base catalyst of a kind of high graphitization degree, high-ratio surface is provided.Namely adopt cheap hard mould agent, take pitch as carbon source, nitrogenous precursor is nitrogenous source, and adds metallic element simultaneously, then through high temperature pyrolysis, nitrogenize, obtains the carbon nano-material of high graphitization degree, high-specific surface area finally by the process such as pickling, ball milling.
Summary of the invention
The object of the present invention is to provide the preparation method of high graphitization degree, high-specific surface area doping carbon base catalyst.
For the preparation method of the high graphitization degree carbon base catalyst of fuel battery negative pole, it take pitch as carbon precursor, after the melting of presoma high-temperature heating, immerses template; After stirring, add nitrogenous precursor wherein, add slaine simultaneously; Then drying, high-temperature process and secondary nitrogenize; Wash in an acidic solution subsequently, removing template; The N doping carbon base catalyst material of high graphitization degree is finally obtained finally by filtration, washing and drying; Its preparation process is:
1) by asphalt heating to softening temperature 40-400 DEG C, make it form melting precursor A;
2) template is joined in A, and Keep agitation, make it to mix, obtain mixture B; Wherein the mass ratio of hard template and pitch is 10:1-1:10, and preferred proportion is 4:1-1:5;
3) in mixture B, add nitrogen-containing precursor, more than Keep agitation 1h, mix, obtain mixture C; Wherein nitrogen-containing precursor and asphalt quality are than being 1:10-1:1000, and wherein preferred proportion is 1:10-1:100;
4) in C, add metal salt solution, continue to stir, obtain mixture D, wherein the mol ratio of slaine and pitch is 1:10-1:100, and preferred proportion is: 1:10-1:40;
5) by mixture D high-temperature process 1 ~ 6 hour under 500 ~ 1800 DEG C of nitriding atmosphere protective conditions, obtain pressed powder E, preferable temperature is 800-1200 DEG C;
6) soaked 24 ~ 50 hours in the acid solution of 0.5 ~ 5M by pressed powder E, cleaning, dry, ball milling, obtain pressed powder F;
7) by pressed powder F high temperature reprocessing 1 ~ 6 hour under 500 DEG C ~ 1800 DEG C nitriding atmosphere protective conditions, obtain carbon base catalyst H of the present invention, preferable temperature is 800 DEG C ~ 1200 DEG C;
Described template is SiO
2colloidal sol, zeolite, Al
2o
3, mesoporous SiO
2, magnesia, magnesium acetate, magnesium gluconate, cupric oxide, zinc oxide, ferrous oxide, di-iron trioxide, calcium carbonate, magnesium carbonate, tri-iron tetroxide, tin ash, silica, aluminium oxide, zirconia, molybdenum trioxide, vanadium trioxide, nano titanium oxide powder, metallic nickel hydroxide, metallic iron hydroxide, the hydroxide of magnesium metal, polystyrene microsphere, one or two or more kinds in poly (methyl methacrylate) micro-sphere.
Described nitrogenous precursor is one or two or more kinds in ethylenediamine, n-hexylamine, trimethylamine, melamine, polyurethane, polypyridine, polypyrrole, polyacrylonitrile, polyaniline, two/melamine resin, Lauxite.
Described slaine is the soluble-salt of one or two or more kinds metallic element in IVB, VB, VIB, VIIB, VIII, IB and IIB race; Soluble-salt is one or two or more kinds in one or more (multiple can cosolvency salt) in the nitrate of metal, carbonate, sulfate, acetate, halide, dinitroso diamine salts, acetylacetonate or large ring complex compound porphyrin, the phthalein mountain valley with clumps of trees and bamboo and polymer thereof; Described metallic element is one or two or more kinds in Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, W, Mo.
Described acid is the one in sulfuric acid, nitric acid, phosphoric acid or hydrochloric acid; Concentration is 0.2M ~ 5M, and preferred concentration is 0.5M ~ 2M.
Described high-temperature process temperature is preferably 800 ~ 1200 DEG C; Described secondary nitriding temperature is preferable temperature 800 ~ 1200 DEG C.
Described nitriding atmosphere is nitrogen, argon gas, helium, NH
3, CH
3one or two or more kinds mixing in CN or HCN gas.
The present invention adopts the pitch of high graphite degree as presoma, utilize cheap hard mould agent, be nitrogenous source with nitrogenous precursor, add metallic element simultaneously, then through high temperature pyrolysis, nitrogenize, the carbon nano-material of high graphitization degree, high-specific surface area is obtained finally by the process such as pickling, ball milling.Take pitch as presoma, not only avoid high temperature graphitization processing procedure, it also avoid the hole caused in high temperature graphitization process and to subside problem; In building-up process, original position adds nitrogenous precursor, original position can introduce the interpolation of nitrogen element and scarce slaine in the defect lattice of catalyst, change the microstructure of Carbon Materials, but also improve N doping degree, add the avtive spot of electrochemical reaction; Adopt hard mould agent, price is cheap, and the material of preparation has high-ratio surface sum height pore volume.Secondary nitrogenize is carried out to prepared material, utilize the corrasion of ammonia, will get rid of the disadvantageous micropore of electrochemical reaction, and the oxygen-containing functional group removing introduced after can also pickling being made, and the content of graphite mould, pyrimidine Type atom N can be changed, enhance the oxygen reduction catalytic activity of catalyst.
The present invention compared with prior art tool has the following advantages:
(1). employ reaction monomers that is cheap, high graphitization, product cost is low, degree of graphitization is high, good conductivity;
(2). in building-up process, original position adds nitrogenous precursor, original position can introduce the interpolation of nitrogen element and scarce slaine in the defect lattice of catalyst, change the microstructure of Carbon Materials, but also improve N doping degree, add the avtive spot of electrochemical reaction;
(3). the material adopting hard mould agent to prepare has high-ratio surface sum height pore volume, adds the avtive spot of catalyst.
(4). prepared material is heat-treated and secondary nitrogenize, utilize the corrasion of ammonia, to get rid of the disadvantageous micropore of electrochemical reaction, and the oxygen-containing functional group removing introduced after can also pickling being made, and the content of graphite mould, pyrimidine Type atom N can be changed, enhance the oxygen reduction catalytic activity of catalyst
(5). provide a kind of preparation method of new metal-loaded catalysis, namely in carbonization process, mix metallic element, metal can not only be made to be dispersed in carbon surface uniformly, and the structure of charcoal can also be changed, thus improve the performance of catalyst.
(6). catalyst has high stability and high activity in acidic fuel cell, and has far away higher than methanol tolerance, CO and SO of Pt/C
2performance.
(7). be used in PEMFC field, also may be used for carrying metal, as platinum etc., and stronger catalytic capability can be provided; And less transition metal can be used, as cobalt, iron etc., show higher oxygen reduction reaction activity and long stability;
(8). preparation method is simple, conventional production device, is applicable to large-scale production.
Accompanying drawing explanation
Fig. 1. the oxygen reduction activity curve comparison of catalyst prepared by the embodiment of the present invention 1 and comparative example.
Detailed description of the invention
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
By 1.0g asphalt heating to softening temperature 200 DEG C, it is made to form melting precursor A; By the CaCO of 50nm nano-scale
3hard template joins in A, and Keep agitation, make it to mix, obtain mixture B, wherein the mass ratio of hard template and pitch is 1:2; In mixture B, add nitrogen-containing precursor, more than Keep agitation 1h, mix, obtain mixture C, wherein oneself two ammoniums of nitrogen-containing precursor are 1:100 with pitch molal weight ratio; In C, add metal salt solution with the ratio that ferric nitrate and pitch mol ratio are 1:30, continue to stir, obtain mixture D; By mixture D in 900 DEG C at NH
3carbonize process under atmosphere protection condition 2 hours, obtain pressed powder E; Soaked 24 hours in the dilute acid soln of 1M by pressed powder E, cleaning, dry, ball milling, obtain carbon base catalyst H of the present invention.
Comparative example 1
By 1.0g asphalt heating to softening temperature 200 DEG C, it is made to form melting precursor A; By the CaCO of 50nm nano-scale
3hard template joins in A, and Keep agitation, make it to mix, obtain mixture B, wherein the mass ratio of hard template and pitch is 1:2; In mixture B, add nitrogen-containing precursor, more than Keep agitation 1h, mix, obtain mixture C, in C, add metal salt solution with the ratio that ferric nitrate and pitch mol ratio are 1:30, continue to stir, obtain mixture D; Mixture D is carbonized process 2 hours under 900 DEG C of nitriding atmosphere protective conditions, obtains pressed powder E; Soaked 24 hours in the dilute acid soln of 1M by pressed powder E, cleaning, dry, ball milling, obtain carbon base catalyst H of the present invention.
Comparative example 2
By 1.0g asphalt heating to softening temperature 200 DEG C, it is made to form melting precursor A; By the CaCO of 50nm nano-scale
3hard template joins in A, and Keep agitation, make it to mix, obtain mixture B, wherein the mass ratio of hard template and pitch is 1:2; In mixture B, add nitrogen-containing precursor, more than Keep agitation 1h, mix, obtain mixture C, wherein oneself two ammoniums of nitrogen-containing precursor are 1:100 with pitch molal weight ratio; By mixture C in 900 DEG C at NH
3carbonize process under atmosphere protection condition 2 hours, obtain pressed powder E; Soaked 24 hours in the dilute acid soln of 1M by pressed powder E, cleaning, dry, ball milling, obtain carbon base catalyst H of the present invention.
In oxygen reduction reaction, the catalytic activity of catalyst adopts rotating disk electrode (r.d.e) (RDE) technical testing, tests and carries out at the potentiostat with EG & G636 rotating disk electrode (r.d.e) controller (Princeton Applied Research).Test condition is as follows: test forward direction 0.5mol L
-1h
2sO
4pass into 30min nitrogen or oxygen in electrolyte, make electrolyte reach oxygen saturation, test the polarization curves of oxygen reduction under two kinds of atmosphere respectively.Sweep limits is 1.14 ~ 0.04V, and sweep speed is 5mV s
-1, electrode rotating speed is 1600rpm.
In order to the anti-oxidant sulphur investigating catalyst poisons ability, when test macro and other test condition are tested identical with aforementioned RDE, changing electrolyte solution is 0.5mol L-1H
2sO
4with 0.1mol L
-1na
2sO
3mixed liquor, after poisoning two minutes, then at 0.5mol L
-1h
2sO
4its polarization curves of oxygen reduction of middle test, poisons front and back polarization curves of oxygen reduction by contrast, evaluates its anti-SO
2antitoxin voltinism energy.
Fig. 1. the catalytic activity of the catalyst prepared according to embodiment 1 compares, rpm=1600; As seen from Figure 1, compared with comparative example 1, the oxygen reduction activity of Carbon Materials prepared by pitch is lower, and after N doping, the performance of catalyst significantly improves.Compared with comparative example 2, after adding metal, the performance of catalyst is apparently higher than the catalyst not adding metal.Catalyst prepared by embodiment 1 has very high oxygen reduction catalytic activity, and its hydrogen reduction starting point is about 0.85V.
Embodiment 2
By 0.5g asphalt heating to softening temperature 280 DEG C, it is made to form melting precursor A; The MgO hard template of 30nm nano-scale is joined in A, and Keep agitation, make it to mix, obtain mixture B, wherein the mass ratio of MgO and pitch is 1:2; In mixture B, add nitrogen-containing precursor melamine, Keep agitation 2h, mixes, and obtains mixture C, and wherein nitrogen-containing precursor and pitch molal weight are than being 1:100; In C, add metal salt solution with the ratio that cobalt nitrate and pitch mol ratio are 1:50, continue to stir, obtain mixture D; Mixture D is carbonized process 2 hours under 800 DEG C of ammonia atmosphere protective conditions, obtains pressed powder E; Soaked 24 hours in the dilute acid soln of 0.5M by pressed powder E, cleaning, dry, ball milling 3h, obtain carbon base catalyst H of the present invention.
Embodiment 3
Pitch 0.5g is heated to softening temperature 180 DEG C, makes it form melting precursor A; By the SiO of 0.5g
2(SBA-15) hard template joins in A, and Keep agitation, make it to mix, obtain mixture B; In mixture B, add nitrogen-containing precursor melamine, Keep agitation 2h, mixes, and obtains mixture C, and wherein nitrogen-containing precursor and pitch molal weight are than being 1:300; In C, add metal salt solution with the ratio that cobalt nitrate and pitch mol ratio are 1:20, continue to stir, obtain mixture D; Mixture D is carbonized process 2 hours under 1000 DEG C of nitriding atmosphere protective conditions, obtains pressed powder E; Soaked 24 hours in the dilute acid soln of 0.5M by pressed powder E, cleaning, dry, ball milling 3h, obtain carbon base catalyst H of the present invention.
Embodiment 4
By 1.5g asphalt heating to softening temperature 260 DEG C, it is made to form melting precursor A; By the CaCO of 50nm nano-scale
3hard template 2g joins in A, and Keep agitation, make it to mix, obtain mixture B; In mixture B, add nitrogen-containing precursor, more than Keep agitation 1h, mix, obtain mixture C, wherein nitrogen-containing precursor second two ammonium and pitch molal weight are than being 1:100; In C, add metal salt solution with the ratio that ferrous nitrate amine and pitch mol ratio are 1:30, continue to stir, obtain mixture D; Mixture D is carbonized process 2 hours under 900 DEG C of nitrogen atmosphere protection conditions, obtains pressed powder E; Soaked 24 hours in the dilute acid soln of 1M by pressed powder E, cleaning, dry, ball milling, obtain carbon base catalyst H of the present invention.
Embodiment 5
By 1.0 asphalt heatings to softening temperature 320 DEG C, it is made to form melting precursor A; By the Al of 80nm nano-scale
2o3 hard template 3.0 joins in A, and Keep agitation, make it to mix, obtain mixture B; Add containing polypyrrole in mixture B, more than Keep agitation 1h, mixes, obtains mixture C, and wherein nitrogen-containing precursor second two ammonium and pitch molal weight are than being 1:100; In C, add metal salt solution with the ratio that ferrous nitrate amine and pitch mol ratio are 1:30, continue to stir, obtain mixture D; Mixture D is carbonized process 2 hours under 800 DEG C of protection of ammonia conditions, obtains pressed powder E; Soaked 24 hours in the dilute acid soln of 1M by pressed powder E, cleaning, dry, ball milling, obtain H.By pressed powder H 800 DEG C of carbonization treatment 1h in nitrogen atmosphere, obtain pressed powder G and be the catalyst that the present invention protects.
Embodiment 6
By 1.0 asphalt heatings to softening temperature 220 DEG C, it is made to form melting precursor A; CaO hard template 3.0g is joined in A, and Keep agitation, make it to mix, obtain mixture B; Add containing polyaniline in mixture B, more than Keep agitation 1h, mixes, obtains mixture C, and wherein nitrogen-containing precursor second two ammonium and pitch molal weight are than being 1:100; In C, add metal salt solution with the ratio that ferrocene and pitch mol ratio are 1:50, continue to stir, obtain mixture D; Mixture D is carbonized process 2 hours under 1000 DEG C of protection of ammonia conditions, obtains pressed powder E; Soaked 24 hours in the dilute acid soln of 1M by pressed powder E, cleaning, dry, ball milling, obtain H.By pressed powder H 900 DEG C of carbonization treatment 1h in ammonia atmosphere, obtain pressed powder G and be the catalyst that the present invention protects.
Claims (7)
1. for the preparation method of the high graphitization degree carbon base catalyst of fuel battery negative pole, it take pitch as carbon precursor, after the melting of presoma high-temperature heating, immerses template; After stirring, add nitrogenous precursor wherein, add slaine simultaneously; Then drying, high-temperature process and secondary nitrogenize; Wash in an acidic solution subsequently, removing template; The N doping carbon base catalyst material of high graphitization degree is finally obtained finally by filtration, washing and drying; Its preparation process is:
1) by asphalt heating to softening temperature 40-400 DEG C, make it form melting precursor A;
2) template is joined in A, and Keep agitation, make it to mix, obtain mixture B; Wherein the mass ratio of hard template and pitch is 10:1-1:10;
3) in mixture B, add nitrogen-containing precursor, Keep agitation is 1h at least, mixes, and obtains mixture C; Wherein nitrogen-containing precursor and asphalt quality are than being 1:10-1:1000;
4) in C, add metal salt solution, continue to stir, obtain mixture D, wherein the mol ratio of slaine and pitch is 1:10-1:100;
5) by mixture D high-temperature process 1 ~ 6 hour under 500 ~ 1800 DEG C of nitriding atmosphere protective conditions, pressed powder E is obtained;
6) soaked 24 ~ 50 hours in the acid solution of 0.5 ~ 5M by pressed powder E, cleaning, dry, ball milling, obtain pressed powder F;
7) by pressed powder F high temperature reprocessing 1 ~ 6 hour under 500 DEG C ~ 1800 DEG C nitriding atmosphere protective conditions, carbon base catalyst H of the present invention is obtained.
2. according to preparation method according to claim 1, it is characterized in that: described template is SiO
2colloidal sol, zeolite, Al
2o
3, mesoporous SiO
2, magnesia, magnesium acetate, magnesium gluconate, cupric oxide, zinc oxide, ferrous oxide, di-iron trioxide, calcium carbonate, magnesium carbonate, tri-iron tetroxide, tin ash, silica, aluminium oxide, zirconia, molybdenum trioxide, vanadium trioxide, nano titanium oxide powder, metallic nickel hydroxide, metallic iron hydroxide, the hydroxide of magnesium metal, polystyrene microsphere, one or two or more kinds in poly (methyl methacrylate) micro-sphere, wherein template grain size scope is at 5 ~ 500nm.
3. according to preparation method according to claim 1, it is characterized in that: described nitrogenous precursor is one or two or more kinds in ethylenediamine, n-hexylamine, trimethylamine, melamine, polyurethane, polypyridine, polypyrrole, polyacrylonitrile, polyaniline, two/melamine resin, Lauxite.
4. according to preparation method according to claim 1, it is characterized in that: described slaine is the soluble-salt of one or two or more kinds metallic element in IVB, VB, VIB, VIIB, VIII, IB and IIB race; Soluble-salt is that one or more in the nitrate of metal, carbonate, sulfate, acetate, halide, dinitroso diamine salts, acetylacetonate or large ring complex compound porphyrin, the phthalein mountain valley with clumps of trees and bamboo and polymer thereof can one or two or more kinds in cosolvency salt; Described metallic element is one or two or more kinds in Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, W, Mo.
5. according to preparation method according to claim 1, it is characterized in that: described acid is the one in sulfuric acid, nitric acid, phosphoric acid or hydrochloric acid; Concentration is 0.2M ~ 5M, and preferred concentration is 0.5M ~ 2M.
6. according to preparation method according to claim 1, it is characterized in that: described high-temperature process temperature is 900 ~ 1100 DEG C; Described secondary nitriding temperature is 900 ~ 1100 DEG C.
7. according to preparation method according to claim 1, it is characterized in that: described nitriding atmosphere is nitrogen, argon gas, helium, NH
3, CH
3one or two or more kinds mixing in CN or HCN gas.
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