CN105742655A - Graded porous carbon material for fuel cell and preparation and application of graded porous carbon material - Google Patents
Graded porous carbon material for fuel cell and preparation and application of graded porous carbon material Download PDFInfo
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Abstract
The invention relates to a graded porous carbon material for a cathode catalyst of a fuel cell. The porous carbon material is a transition metal-nitrogen-fluorine/carbon ordered graded porous material and is prepared through a solvent evaporation-induced self-assembly process; the specific surface area is 500-1200m<2>.g<-1>; the total pore volume is 0.5-2cm<3>g.<-1>; the mesopore volume accounts for 30%-70% of total pore volume; the atom content of the transition metal is 0.1-1wt%; the atom content of nitrogen is 1-5wt%; and the atom content of fluorine is 0.1-0.5wt%. The metal iron, fluorine and nitrogen-co-doped ordered graded porous carbon material demonstrates excellent oxygen-reducing catalytic performance and has good stability. The carbon material provided by the invention has the advantages of being excellent in preparation property, simple in process, good in process repeatability, low in cost, friendly to environment and the like.
Description
Technical field
The present invention relates to field of fuel cell technology, specifically a kind of ferrum, fluorine, nitrogen co-doped orderly classifying porous material and the application on fuel battery cathod catalyst thereof.
Background technology
The energy is the basis of progress of social civilization and the national economic development.In recent years, along with socioeconomic progress, people are growing to the demand of the energy, and meanwhile, due to a large amount of uses of fossil energy, create substantial amounts of nitrogen oxides and oxysulfide so that environmental problem is day by day serious.Cannot having met contemporary society to efficiently based on the traditional energy structure of the Fossil fuels such as coal, oil, natural gas, cleaning, the demand of economic new energy system, energy development is faced with unprecedented challenge.
Owing to fuel cell has the advantages such as fast response time, energy conversion efficiency is high, energy density is high and environment friendly and pollution-free, it has the application prospect of light in fields such as portable power source, stationary electric power plant, distributing power station and Military Powers.Through the effort of researcher decades, the critical material of fuel cell is broken through, it is thus achieved that significant progress.But, current fuel cell does not but obtain large-scale commercial applications all the time, and the cost of its costliness is an important reason.Although through effort in the past few decades, the cost of fuel cell fell below the $ 61/KW of 2009 from the $ 275/KW of 2002, but the practical application target of the $ 30/KW of distance USDOE proposition also has certain distance.
One of critical material as fuel cell, platinum based catalyst, due to its resource scarcity, cost intensive, becomes one of key factor of obstruction fuel cell industrialization process.Therefore, in order to reduce catalyst cost, it is achieved the commercialization of fuel cell, researching and developing cheap non-precious metal catalyst is a only way which must be passed.At present, although having developed a series of non-precious metal catalyst, such as metal nitride, oxide, metal carbides and chelate etc., but its activity and stability are catalyst based far below Pt, also have very big gap from application request.
Carbon nanomaterial has very unique catalytic action on molecule nano yardstick, shows using value in a lot of fields, causes the great attention of researcher.Research in recent years shows, some hetero atoms that adulterate, as nitrogen-atoms, phosphorus atoms, sulphur atom, boron atom material with carbon element in oxygen reduction reaction, show higher oxygen reduction catalytic activity.Researcheres think that the hetero atom of doping changes microstructure and the surface electronic state of carbon nanomaterial, weaken the O--O bond of oxygen molecule, thus there is oxygen reduction reaction.Meanwhile, researcheres find, the material with carbon element after Heteroatom doping is different from pore structure according to its specific surface, and catalysis activities present goes out larger difference.Therefore develop the Heteroatom doping nano-carbon material with high-ratio surface and suitable pore structure and become one of study hotspot as high performance fuel cell catalyst.
Summary of the invention
It is an object of the invention to provide a kind of ferrum, fluorine, nitrogen co-doped orderly classifying porous material with carbon element and preparation method thereof and be applied to fuel battery negative pole oxygen reduction reaction catalysis.
For achieving the above object, the technical solution used in the present invention is as follows:
Described fuel battery cathod catalyst is a kind of transition metal-orderly classifying porous material of nitrogen-fluorine/carbon, described porous carbon materials is the orderly classifying porous material of transition metal-nitrogen-fluorine/carbon, being made by solvent evaporation induced self-assembly process, specific surface area is 500-1200m2.g-1, total hole volume is 0.5-2cm3.g-1, wherein mesoporous volume accounts for total hole volume ratio is 30-70, and transition metal atoms content is 0.1-1wt%, and nitrogen atom content is 1-5wt%, and fluorine atom content is 0.1-0.5wt%.
The concrete preparation method of described porous carbon materials is as follows:
Formulated phenolic resin performed polymer alcoholic solution, mass concentration is 0.3g.mL-1；
Performed polymer and soft template are sufficiently mixed in proportion, in mixed solution, add transition metal iron salt precursor thing and organic fluorocompound, pour into after mixing in culture dish, after after solvent volatilization, put into oven drying；Dried product exhibited is taken out, under ammonia atmosphere, sinters 1-2h in 700-900 DEG C, by ball-milling treatment.
Described phenolic resin performed polymer is phenol and one or both hybrid resin performed polymers in formaldehyde reaction gained resin prepolymer, resorcinol and formaldehyde reaction gained resin prepolymer；
Transition metal salt solution is one or two or more kinds in the sulfate of ferrum, nitrate or Chloride Solution；Organic fluorocompound is the fluoro-3-fluoro-2-methyl aniline of 2-；
In performed polymer, the mol ratio of phenol and/or resorcinol and soft template is 20:1-100:1；
In performed polymer, the ratio of phenol and/or resorcinol and iron content presoma is 10:1-60:1；
In performed polymer, the ratio of phenol and/or resorcinol and organic fluorocompound is 0.25:1-4:1；
Soft template is F127 or P123.
Described porous carbon materials is used as fuel battery cathod catalyst.
Beneficial effects of the present invention:
1. ferrum provided by the invention, fluorine, nitrogen co-doped orderly classifying porous material with carbon element are prepared with solvent evaporation induced self-assembly process, raw material is easy to get, cheap, preparation technology is simple compared with conventional porous material with carbon element, it is easy to accomplish the regulation and control of contrast surface, pore structure and pore-size distribution.
2. ferrum provided by the invention, fluorine, nitrogen co-doped orderly classifying porous material with carbon element adopt soluble resin macromolecule as carbon source, by adding metal salt solution and organic fluorocompound kind, induce in template and self assembling process introduces metallic atom and fluorine atom, avoid follow-up doping treatment, simplify preparation process.
3. having significantly high oxygen reduction catalytic activity when the ferrum that prepared by preparation method of the present invention, fluorine, nitrogen co-doped orderly classifying porous material with carbon element are for fuel battery cathod catalyst, this material list reveals stability and the mithridatism of excellence simultaneously.
4. the introducing of soft template in the present invention, is effectively improved material specific surface area, and induction produces orderly graded porous structure, provides more avtive spot in fuel battery negative pole oxygen reduction reaction process, and pore structure effectively facilitates mass transfer in order simultaneously, carries stability of material.
Accompanying drawing explanation
Fig. 1 be embodiment 1 obtain ferrum, fluorine, nitrogen co-doped orderly classifying porous material with carbon element TEM image.
Fig. 2 be embodiment 2 obtain ferrum, fluorine, nitrogen co-doped orderly classifying porous material with carbon element with do not add template obtain material at 0.5MH2SO4In solution, under oxygen is saturated, sweep the linear sweep voltammetry curve of speed 10mV/s.
Fig. 3 be embodiment 2 obtain ferrum, fluorine, nitrogen co-doped orderly classifying porous material with carbon element is at 0.5MH2SO4In solution, under oxygen is saturated, before and after accelerated aging test, sweep the linear sweep voltammetry curve of speed 10mV/s.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the enforcement of the present invention is not limited only to this.
In following example, material oxygen reduction reaction electrochemical test method is as follows:
Cyclic voltammetric (CV) performance of catalyst adopts CHI600B (CHCorp.) potentiostat, tests under tradition three-electrode system.The preparation flow of working electrode is as follows: by 5mg catalyst sample, 1mL isopropanol and the 50 μ ultrasonic mixing of L5wt.%Nafion solution, form uniform slurry.Remove 10 μ L slurries from which to be transferred to area be 0.1256cm with microsyringe2Glass-carbon electrode on, dry formation membrane electrode.On electrode, the dead weight capacity of catalyst sample is 0.379mgcm-2.Reference electrode and to electrode respectively saturated KCl calomel electrode (SCE, the current potential relative to reversible hydrogen electrode RHE is 0.242V) and Pt plate electrode (3cm2), electrolyte is 0.5MH2SO4Solution.Room temperature test, first leads to 30min high pure nitrogen, the oxygen of the dissolving in removing solution in electrolyte before test.Electric potential scanning ranges for-0.25～0.96Vvs.SCE, and scanning speed is 50mVs-1。
In oxygen reduction reaction, the catalysis activity of catalyst adopts rotating disk electrode (r.d.e) (RDE) technical testing, and experiment carries out on the CHI600B potentiostat with EG&G636 rotating disk electrode (r.d.e) controller (PrincetonAppliedResearch).Test condition is identical with CV test with environment, tests forward direction 0.5MH2SO4Electrolyte passes into 30min oxygen, makes electrolyte reach oxygen saturation.Sweep limits is-0.2～0.9Vvs.SCE, and scanning speed is 10mVs-1, and electrode rotating speed is 1600rpm.
In following example, the accelerated aging test method of material is as follows:
At the saturated 0.5MH of nitrogen2SO4Being circulated voltammetric scan in solution, scanning speed is 50mV/s, after 1000 circles, 2000 circle scannings, at the saturated 0.5MH of oxygen2SO4In solution, scanning speed is 10mV/s, carries out linear voltammetric scan respectively.
Embodiment 1
(1) preparation of phenolic resin performed polymer:
2g phenol is melted at 50 DEG C, add 0.5g20wt.%NaOH aqueous solution stirring 10min, the formalin instilling 3.5g37wt.% continues stirring 10min, it is to slowly warm up to 75 DEG C of reaction 30min, it is cooled to room temperature, the pH value regulating solution with rare HCl solution is 7.0, reduce the water content in thick liquid at 45 DEG C of decompression distillation 1 4h as far as possible, the resol resin performed polymer obtained is dissolved in ethanol stir overnight 12h, the sodium chloride centrifugation precipitated out is removed, finally joins to obtain resol resin performed polymer alcoholic solution (0.3g.mL-1) stand-by.
(2) preparation of ferrum, fluorine, nitrogen co-doped orderly classifying porous material with carbon element
Being dissolved in by 0.8gF127 in 20g ethanol, stir to clarify transparent, be subsequently adding 4g phenolic resin performed polymer alcoholic solution, controlling phenol with F127 mol ratio is 80:1, and stirring 10min obtains homogeneous solution.0.09gFeSO4 7H is added in solution2O (phenol and FeSO4 7H2O mol ratio is 20:1) and the fluoro-3-fluoro-2-methyl aniline of 0.48g2-(phenol and its mol ratio are 1:1).Transferring in culture dish by this solution, at room temperature volatilize 6h, then culture dish is placed in 100 DEG C of oven for curing 24h, obtains transparent thin-film material.This material is scraped from culture dish, grind into powder, obtain the polymer composite of ordered structure.Sample is placed in tube furnace, under ammonia atmosphere, 800 DEG C of high-temperature roasting solution 2h, obtain orderly classifying porous material with carbon element.In roasting process, ammonia flow is 60mL/min, and heating rate is 1 DEG C/min.
Ferrum as shown in Figure 1, fluorine, nitrogen co-doped orderly classifying porous material with carbon element TEM picture show that it has ordered mesopore structure, edge causes that disordered structure produces due to ammonia atmosphere carbonization simultaneously.
Embodiment 2
(1) preparation of phenolic resin performed polymer:
2g phenol is melted at 50 DEG C, add 0.5g20wt.%NaOH aqueous solution stirring 10min, the formalin instilling 3.5g37wt.% continues stirring 10min, it is to slowly warm up to 75 DEG C of reaction 30min, it is cooled to room temperature, the pH value regulating solution with rare HCl solution is 7.0, reduce the water content in thick liquid at 45 DEG C of decompression distillation 1 4h as far as possible, the resol resin performed polymer obtained is dissolved in ethanol stir overnight 12h, the sodium chloride centrifugation precipitated out is removed, finally joins to obtain resol resin performed polymer alcoholic solution (0.3g.mL-1) stand-by.
(2) preparation of ferrum, fluorine, nitrogen co-doped orderly classifying porous material with carbon element
Being dissolved in by 1.6gF127 in 20g ethanol, stir to clarify transparent, be subsequently adding 4g phenolic resin performed polymer alcoholic solution, controlling phenol with F127 mol ratio is 40:1, and stirring 10min obtains homogeneous solution.0.03gFeSO4 7H is added in solution2O (phenol and FeSO4 7H2O mol ratio is 60:1) and the fluoro-3-fluoro-2-methyl aniline of 0.24g2-(phenol and its mol ratio are 2:1).Transferring in culture dish by this solution, at room temperature volatilize 6h, then culture dish is placed in 100 DEG C of oven for curing 24h, obtains transparent thin-film material.This material is scraped from culture dish, grind into powder, obtain the polymer composite of ordered structure.Sample is placed in tube furnace, under ammonia atmosphere, 800 DEG C of high-temperature roasting solution 2h, obtain orderly classifying porous material with carbon element.In roasting process, ammonia flow is 60mL/min, and heating rate is 1 DEG C/min.
Products therefrom is carried out electro-chemical test.Ferrum as shown in Figure 2, fluorine, nitrogen co-doped orderly classifying porous material with carbon element are as oxygen reduction catalyst, and in reaction, hydrogen reduction take-off potential is 0.79V, and carrying current is 4.3mAcm-2, it is significantly improved compared to the material catalytic performance not adding soft template.Shown in Fig. 3, after 1000 enclose cyclic voltammetry scan, material hydrogen reduction catalytic performance is without obvious decay.
Embodiment 3
(1) preparation of phenolic resin performed polymer:
2.2g resorcinol is melted at 50 DEG C, add 0.5g20wt.%NaOH aqueous solution stirring 10min, the formalin instilling 3.5g37wt.% continues stirring 10min, it is to slowly warm up to 75 DEG C of reaction 30min, it is cooled to room temperature, the pH value regulating solution with rare HCl solution is 7.0, reduce the water content in thick liquid at 45 DEG C of decompression distillation 1 4h as far as possible, the resol resin performed polymer obtained is dissolved in ethanol stir overnight 12h, the sodium chloride centrifugation precipitated out is removed, finally joins to obtain resol resin performed polymer alcoholic solution (0.3g.mL-1) stand-by.
(2) preparation of ferrum, fluorine, nitrogen co-doped orderly classifying porous material with carbon element
Being dissolved in by 2.1gP123 in 20g ethanol, stir to clarify transparent, be subsequently adding 4g phenolic resin performed polymer alcoholic solution, controlling phenol with F127 mol ratio is 40:1, and stirring 10min obtains homogeneous solution.0.04gFeCl is added in solution3(phenol and FeCl3Mol ratio is 20:1) and the fluoro-3-fluoro-2-methyl aniline of 0.24g2-(phenol and its mol ratio are 2:1).Transferring in culture dish by this solution, at room temperature volatilize 6h, then culture dish is placed in 100 DEG C of oven for curing 24h, obtains transparent thin-film material.This material is scraped from culture dish, grind into powder, obtain the polymer composite of ordered structure.Sample is placed in tube furnace, under ammonia atmosphere, 800 DEG C of high-temperature roasting solution 2h, obtain orderly classifying porous material with carbon element.In roasting process, ammonia flow is 60mL/min, and heating rate is 1 DEG C/min.
The invention discloses a kind of ferrum, fluorine, the preparation method of nitrogen co-doped orderly classifying porous material with carbon element and application in fuel cell oxygen reduction catalytic reaction thereof.This porous material is to be made by soft template method simply, using triblock copolymer as template, select soluble resin as carbon source, preparation process is added metallic and organic fluorocompound, thus original position can introduce metallic atom and fluorine atom, introduce nitrogen element by ammonia atmosphere roasting simultaneously.This aufe, fluorine, nitrogen co-doped orderly classifying porous material with carbon element present the hydrogen reduction catalytic performance of excellence, are provided simultaneously with good stability.The material with carbon element of the present invention, has processability excellence, technique is simple, good process repeatability, cost are low and advantages of environment protection.
Claims (4)
1. the classifying porous material with carbon element of fuel battery cathod catalyst, it is characterised in that: described porous carbon materials is the orderly classifying porous material of transition metal-nitrogen-fluorine/carbon, is made by solvent evaporation induced self-assembly process, and specific surface area is 500-1200m2.g-1, total hole volume is 0.5-2cm3.g-1, wherein mesoporous volume accounts for total hole volume ratio is 30-70, and transition metal atoms content is 0.1-1wt%, and nitrogen atom content is 1-5wt%, and fluorine atom content is 0.1-0.5wt%.
2. the preparation method of the porous carbon materials described in a claim 1, it is characterised in that the concrete preparation method of described porous carbon materials is as follows:
1) formulated phenolic resin performed polymer alcoholic solution, mass concentration is 0.3g.mL-1；
2) performed polymer and soft template are sufficiently mixed in proportion, in mixed solution, add transition metal iron salt precursor thing and organic fluorocompound, pour into after mixing in culture dish, after after solvent volatilization, put into oven drying；Dried product exhibited is taken out, under ammonia atmosphere, sinters 1-2h in 700-900 DEG C, by ball-milling treatment.
3. the preparation method of porous carbon materials as claimed in claim 2, it is characterised in that
Described phenolic resin performed polymer is phenol and one or both hybrid resin performed polymers in formaldehyde reaction gained resin prepolymer, resorcinol and formaldehyde reaction gained resin prepolymer；
Transition metal salt solution is one or two or more kinds in the sulfate of ferrum, nitrate or Chloride Solution；Organic fluorocompound is the fluoro-3-fluoro-2-methyl aniline of 2-；
In performed polymer, the mol ratio of phenol and/or resorcinol and soft template is 20:1-100:1；
In performed polymer, the ratio of phenol and/or resorcinol and iron content presoma is 10:1-60:1；
In performed polymer, the ratio of phenol and/or resorcinol and organic fluorocompound is 0.25:1-4:1；
Soft template is F127 or P123.
4. the application in a fuel cell of the porous carbon materials described in a claim 1, it is characterised in that: described porous carbon materials is used as fuel battery cathod catalyst.
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