CN105742655B - A kind of classifying porous carbon material of fuel cell and its preparation and application - Google Patents
A kind of classifying porous carbon material of fuel cell and its preparation and application Download PDFInfo
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- CN105742655B CN105742655B CN201410764356.2A CN201410764356A CN105742655B CN 105742655 B CN105742655 B CN 105742655B CN 201410764356 A CN201410764356 A CN 201410764356A CN 105742655 B CN105742655 B CN 105742655B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The present invention relates to a kind of classifying porous carbon material of fuel battery cathod catalyst, the porous carbon materials are the orderly classifying porous material of transition metal-nitrogen-fluorine/carbon, are made up of solvent evaporation induced self-assembly process, specific surface area 500-1200m2.g‑1, total hole volume is 0.5-2 ㎝3.g‑1, it is 30-70 ﹪ that wherein mesoporous volume, which accounts for total hole volume ratio, and transition metal atoms content is 0.1-1wt%, nitrogen atom content 1-5wt%, fluorine atom content 0.1-0.5wt%.The gold iron, fluorine, nitrogen co-doped orderly classifying porous carbon material present excellent hydrogen reduction catalytic performance, are provided simultaneously with good stability.The carbon material of the present invention has excellent processability, simple for process, good process repeatability, at low cost and advantages of environment protection.
Description
Technical field
The present invention relates to field of fuel cell technology, specifically a kind of iron, fluorine, it is nitrogen co-doped orderly classifying porous material and
Its application on fuel battery cathod catalyst.
Background technology
The energy is the basis of progress of social civilization and the national economic development.In recent years, with the progress of social economy, people
Demand to the energy is growing, and at the same time, due to a large amount of uses of fossil energy, produce a large amount of nitrogen oxides and
Oxysulfide so that environmental problem getting worse.Traditional energy knot based on the fossil fuels such as coal, oil, natural gas
Structure can no longer meet contemporary society to efficient, cleaning, the demand of economic new energy system, before energy development is faced with
The challenge not having.
Since fuel cell has, fast response time, energy conversion efficiency are high, energy density is high and environment friendly and pollution-free etc. excellent
Point has bright application prospect in fields such as mobile power, stationary electric power plant, distributing power station and Military Powers.By
The critical material of the effort of researcher's decades, fuel cell is broken through, and significant progress is obtained.However, current fuel
Battery does not obtain large-scale commercial applications but always, and expensive cost is an important reason.Although by
Go the effort of decades, the cost of fuel cell fell below $ 61/KW in 2009 from $ 275/KW in 2002, but away from
The practical application target of $ 30/KW from U.S. Department of Energy proposition also has a certain distance.
One of critical material as fuel cell, platinum based catalyst is expensive due to its resource scarcity, becomes resistance
One of an important factor for hindering fuel cell industrialization process.Therefore, in order to reduce catalyst cost, the business of fuel cell is realized
Change, it is a only way which must be passed to research and develop cheap non-precious metal catalyst.Currently, although having developed a series of base metals
Catalyst, such as metal nitride, oxide, metal carbides and chelate, but its activity and stability are far below Pt
Base catalyst also has prodigious gap from application request.
Carbon nanomaterial has very unique catalytic action on molecule nano scale, shows and answers in many fields
With value, the great attention of researcher is caused.In recent years studies have shown that some doping hetero atoms, such as nitrogen-atoms, phosphorus
Atom, sulphur atom, boron atom carbon material in oxygen reduction reaction, show higher oxygen reduction catalytic activity.Researchers
Think that the hetero atom of doping changes the microstructure and surface electronic state of carbon nanomaterial, weakens the O -- O bond of oxygen molecule, from
And oxygen reduction reaction occurs.At the same time, researchers have found, the carbon material after Heteroatom doping is tied according to its specific surface and hole
The difference of structure, catalytic activity show larger difference.Therefore Heteroatom doping of the exploitation with high-ratio surface and suitable for pore structure
Nano-carbon material, which is used as high performance fuel cell catalyst, becomes one of research hotspot.
Invention content
The purpose of the present invention is to provide a kind of iron, fluorine, nitrogen co-doped orderly classifying porous carbon material and preparation method thereof,
And it is applied to the catalysis of fuel battery negative pole oxygen reduction reaction.
To achieve the above object, the technical solution adopted by the present invention is as follows：
The fuel battery cathod catalyst is a kind of transition metal-nitrogen-fluorine/carbon orderly classifying porous material, described
Porous carbon materials be transition metal-nitrogen-fluorine/carbon orderly classifying porous material, pass through solvent evaporation induced self-assembly process
It is made, specific surface area 500-1200m2.g-1, total hole volume 0.5-2cm3.g-1, wherein mesoporous volume accounts for total hole volume ratio
For 30-70 ﹪, transition metal atoms content is 0.1-1wt%, nitrogen atom content 1-5wt%, fluorine atom content 0.1-
0.5wt%.
The specific preparation method of the porous carbon materials is as follows：
Formulated phenolic resin performed polymer ethanol solution, mass concentration 0.3g.mL-1；
Performed polymer is sufficiently mixed in proportion with soft template, into mixed solution be added transition metal iron salt precursor object and
Organic fluorocompound pours into after mixing in culture dish, solvent volatilize after after be put into oven drying；Dried product exhibited is taken out,
It is sintered 1-2h in 700-900 DEG C under ammonia atmosphere, by ball-milling treatment.
The phenolic resin performed polymer reacts gained resin prepolymer for phenol with formaldehyde, resorcinol reacts institute with formaldehyde
Obtain one or both of resin prepolymer hybrid resin performed polymer；
Transition metal salt solution is the one or two or more kinds in the sulfate, nitrate or Chloride Solution of iron；It is fluorine-containing
Organic matter is the fluoro- 3- fluoro-2-methyls aniline of 2-；
The molar ratio of phenol and/or resorcinol and soft template is 20 in performed polymer:1-100:1；
The ratio of phenol and/or resorcinol and iron content presoma is 10 in performed polymer:1-60:1；
The ratio of phenol and/or resorcinol and organic fluorocompound is 0.25 in performed polymer:1-4:1；
Soft template is F127 or P123.
The porous carbon materials are used as fuel battery cathod catalyst.
Beneficial effects of the present invention：
1. iron provided by the invention, fluorine, nitrogen co-doped orderly classifying porous carbon material are with solvent evaporation induced self-assembly
Prepared by process, raw material is easy to get, cheap, and preparation process is simple compared with conventional porous carbon material, it is easy to accomplish contrast table
The regulation and control in face, pore structure and pore-size distribution.
2. iron provided by the invention, fluorine, nitrogen co-doped orderly classifying porous carbon material are made using soluble resin macromolecule
For carbon source metallic atom is introduced in template induces self assembling process by adding metal salt solution and organic fluorocompound kind
And fluorine atom, follow-up doping treatment is avoided, preparation process is simplified.
3. iron prepared by preparation method of the present invention, fluorine, nitrogen co-doped orderly classifying porous carbon material are for fuel electricity
With very high oxygen reduction catalytic activity when pool cathode catalyst, while the material shows excellent stability and mithridatism.
4. the introducing of soft template in the present invention effectively improves material specific surface area, induction generates orderly graded porous structure,
More active sites are provided during fuel battery negative pole oxygen reduction reaction, while orderly pore structure effectively facilitates biography
Matter carries stability of material.
Description of the drawings
Fig. 1 be embodiment 1 obtain iron, fluorine, it is nitrogen co-doped orderly classifying porous carbon material TEM image.
Fig. 2 is that iron, fluorine, the nitrogen co-doped orderly classifying porous carbon material that embodiment 2 obtains are obtained with template is not added
Material in 0.5M H2SO4In solution, under oxygen saturation, the linear sweep voltammetry curve of fast 10mV/s is swept.
Fig. 3 be embodiment 2 obtain iron, fluorine, it is nitrogen co-doped orderly classifying porous carbon material in 0.5M H2SO4In solution,
Under oxygen saturation, before and after accelerated aging test, the linear sweep voltammetry curve of fast 10mV/s is swept.
Specific implementation mode
With reference to embodiment, the invention will be further described, but the implementation of the present invention is not limited only to this.
Material oxygen reduction reaction electrochemical test method is as follows in following embodiment：
Cyclic voltammetric (CV) performance of catalyst uses CHI 600B (CH Corp.) potentiostat, in traditional three electrode bodies
It is tested under system.The preparation flow of working electrode is as follows：By 5mg catalyst samples, 1mL isopropanols and 50 μ L 5wt.%
Nafion solution ultrasonic mixing forms uniform slurry.It is from wherein removing 10 μ L slurries and be transferred to area with microsyringe
0.1256cm2Glass-carbon electrode on, dry to form membrane electrode.The dead weight capacity of catalyst sample is 0.379mg cm on electrode-2。
Reference electrode and be respectively to be saturated KCl calomel electrodes to electrode (SCE, the current potential relative to reversible hydrogen electrode RHE are 0.242V)
With Pt plate electrodes (3cm2), electrolyte is 0.5M H2SO4Solution.Room temperature is tested, and it is high-purity first to lead to 30min before testing into electrolyte
Nitrogen removes the oxygen of the dissolving in solution.Electric potential scanning ranging from -0.25~0.96V vs.SCE, sweep speed are 50mV s-1。
The catalytic activity of catalyst uses rotating disk electrode (r.d.e) (RDE) technical testing in oxygen reduction reaction, tests attached
There are the CHI 600B potentiostats of EG&G636 rotating disk electrode (r.d.e)s controller (Princeton Applied Research) enterprising
Row.Test condition and environment are identical as CV tests, to 0.5M H before test2SO4It is passed through 30min oxygen in electrolyte, makes electrolyte
Reach oxygen saturation.Scanning range is -0.2~0.9V vs.SCE, and sweep speed is 10mV s-1, and electrode rotating speed is 1600rpm.
The accelerated aging test method of material is as follows in following embodiment：
In nitrogen saturation 0.5M H2SO4Cyclic voltammetry scan, sweep speed 50mV/s, by 1000 are carried out in solution
After circle, 2000 circle scannings, in oxygen saturation 0.5M H2SO4In solution, sweep speed 10mV/s carries out linear volt-ampere and sweeps respectively
It retouches.
Embodiment 1
(1) preparation of phenolic resin performed polymer:
2g phenol is melted at 50 DEG C, 0.5g 20wt.%NaOH aqueous solutions are added and stir 10min, instill 3.5g
The formalin of 37wt.% continues to stir 10min, is to slowly warm up to 75 DEG C of reaction 30min, is cooled to room temperature, molten with dilute HCl
The pH value that liquid adjusts solution is 7.0, and 1-4h is evaporated under reduced pressure at 45 DEG C reduces the water content in thick liquid as possible, by what is obtained
Resol resin performed polymer is dissolved in ethyl alcohol and stirs evenly overnight 12h, and the sodium chloride of precipitation is centrifuged and is removed, is finally matched
Obtain resol resin performed polymer ethanol solution (0.3g.mL-1) for use.
(2) preparation of iron, fluorine, nitrogen co-doped orderly classifying porous carbon material
0.8g F127 are dissolved in 20g ethyl alcohol, stir to clarify it is transparent, then be added 4g phenolic resin performed polymer second
Alcoholic solution, control phenol are 80 with F127 molar ratios：1, stirring 10min obtains homogeneous solution.0.09g is added into solution
FeSO4·7H2O (phenol and FeSO47H2O molar ratios are 20:1) and the fluoro- 3- fluoro-2-methyls aniline of 0.48g 2- (phenol and its
Molar ratio is 1:1).The solution is transferred in culture dish, volatilize 6h at room temperature, then culture dish is placed in 100 DEG C of baking ovens
Solidification for 24 hours, obtains transparent thin-film material.The material is scraped, grind into powder from culture dish, obtains the high score of ordered structure
Sub- compound.Sample is placed in tube furnace, under ammonia atmosphere, 800 DEG C of high-temperature roasting solution 2h obtain orderly graded porous carbon
Material.In roasting process, ammonia flow 60mL/min, heating rate is 1 DEG C/min.
Iron as shown in Figure 1, fluorine, nitrogen co-doped orderly classifying porous carbon material TEM pictures show that it has and be orderly situated between
Pore structure, while edge causes disordered structure to generate since ammonia atmosphere is carbonized.
Embodiment 2
(1) preparation of phenolic resin performed polymer:
2g phenol is melted at 50 DEG C, 0.5g 20wt.%NaOH aqueous solutions are added and stir 10min, instill 3.5g
The formalin of 37wt.% continues to stir 10min, is to slowly warm up to 75 DEG C of reaction 30min, is cooled to room temperature, molten with dilute HCl
The pH value that liquid adjusts solution is 7.0, and 1-4h is evaporated under reduced pressure at 45 DEG C reduces the water content in thick liquid as possible, by what is obtained
Resol resin performed polymer is dissolved in ethyl alcohol and stirs evenly overnight 12h, and the sodium chloride of precipitation is centrifuged and is removed, is finally matched
Obtain resol resin performed polymer ethanol solution (0.3g.mL-1) for use.
(2) preparation of iron, fluorine, nitrogen co-doped orderly classifying porous carbon material
1.6g F127 are dissolved in 20g ethyl alcohol, stir to clarify it is transparent, then be added 4g phenolic resin performed polymer second
Alcoholic solution, control phenol are 40 with F127 molar ratios：1, stirring 10min obtains homogeneous solution.0.03g is added into solution
FeSO4·7H2O (phenol and FeSO47H2O molar ratios are 60:1) and the fluoro- 3- fluoro-2-methyls aniline of 0.24g 2- (phenol and its
Molar ratio is 2:1).The solution is transferred in culture dish, volatilize 6h at room temperature, then culture dish is placed in 100 DEG C of baking ovens
Solidification for 24 hours, obtains transparent thin-film material.The material is scraped, grind into powder from culture dish, obtains the high score of ordered structure
Sub- compound.Sample is placed in tube furnace, under ammonia atmosphere, 800 DEG C of high-temperature roasting solution 2h obtain orderly graded porous carbon
Material.In roasting process, ammonia flow 60mL/min, heating rate is 1 DEG C/min.
Products therefrom is subjected to electro-chemical test.Iron as shown in Figure 2, fluorine, nitrogen co-doped orderly classifying porous carbon material
As oxygen reduction catalyst, hydrogen reduction take-off potential is 0.79V in reaction, and carrying current is 4.3mA cm-2, compared to not being added
The material catalytic performance of soft template is significantly improved.Shown in Fig. 3, after 1000 circle cyclic voltammetry scans, material hydrogen reduction is urged
Change performance without apparent decaying.
Embodiment 3
(1) preparation of phenolic resin performed polymer:
2.2g resorcinols are melted at 50 DEG C, 0.5g 20wt.%NaOH aqueous solutions are added and stir 10min, instill
The formalin of 3.5g 37wt.% continues to stir 10min, is to slowly warm up to 75 DEG C of reaction 30min, is cooled to room temperature, use is dilute
The pH value that HCl solution adjusts solution is 7.0, and 1-4h is evaporated under reduced pressure at 45 DEG C reduces the water content in thick liquid as possible, will
To resol resin performed polymer be dissolved in ethyl alcohol and stir evenly overnight 12h, the sodium chloride of precipitation is centrifuged and is removed, most
Match to obtain resol resin performed polymer ethanol solution (0.3g.mL afterwards-1) for use.
(2) preparation of iron, fluorine, nitrogen co-doped orderly classifying porous carbon material
2.1g P123 are dissolved in 20g ethyl alcohol, stir to clarify it is transparent, then be added 4g phenolic resin performed polymer second
Alcoholic solution, control phenol are 40 with F127 molar ratios：1, stirring 10min obtains homogeneous solution.0.04g is added into solution
FeCl3(phenol and FeCl3Molar ratio is 20:1) and the fluoro- 3- fluoro-2-methyls aniline of 0.24g 2- (phenol and its molar ratio are 2:1).
The solution is transferred in culture dish, volatilize 6h at room temperature, then by culture dish be placed in 100 DEG C it is oven for curing for 24 hours, obtain
Bright thin-film material.The material is scraped, grind into powder from culture dish, obtains the polymer composite of ordered structure.By sample
Product are placed in tube furnace, and under ammonia atmosphere, 800 DEG C of high-temperature roasting solution 2h obtain orderly classifying porous carbon material.Roasting process
In, ammonia flow 60mL/min, heating rate is 1 DEG C/min.
The invention discloses a kind of iron, fluorine, it is nitrogen co-doped orderly classifying porous carbon material preparation method and its in fuel
Application in battery hydrogen reduction catalysis reaction.The porous material is made of by simply soft template method, with triblock copolymer
It as template, selects soluble resin as carbon source, metallic and organic fluorocompound is added in preparation process, thus can
Metallic atom and fluorine atom are introduced in situ, while being roasted by ammonia atmosphere and introducing nitrogen.It is the gold iron, fluorine, nitrogen co-doped
Orderly classifying porous carbon material presents excellent hydrogen reduction catalytic performance, is provided simultaneously with good stability.The carbon of the present invention
Material has excellent processability, simple for process, good process repeatability, at low cost and advantages of environment protection.
Claims (2)
1. a kind of application of classifying porous carbon material as cathod catalyst in a fuel cell, it is characterised in that：Described is more
Hole carbon material is the orderly classifying porous material of iron-nitrogen-fluorine/carbon, is made up of solvent evaporation induced self-assembly process, specific surface
Product is 500-1200 ㎡ .g-1, and total hole volume is 0.5-2 ㎝ 3.g-1, and it is 30- that wherein mesoporous volume, which accounts for total hole volume ratio,
70 ﹪, iron atom content are 0.1-1wt%, nitrogen atom content 1-5wt%, fluorine atom content 0.1-0.5wt%；It is described more
The specific preparation method of hole carbon material is as follows：
1）Formulated phenolic resin performed polymer ethanol solution, mass concentration are 0.3 g. mL-1；
2）Performed polymer is sufficiently mixed in proportion with soft template, transition metal molysite and fluorine-containing organic is added into mixed solution
Object pours into after mixing in culture dish, and solvent is put into oven drying after volatilizing；Dried product exhibited is taken out, in ammonia atmosphere
Under in 700-900 DEG C be sintered 1-2h, by ball-milling treatment；
Wherein organic fluorocompound is the fluoro- 3- fluoro-2-methyls aniline of 2-, and soft template is F127 or P123.
2. the application as described in claim 1, which is characterized in that the phenolic resin performed polymer reacts institute with formaldehyde for phenol
Obtain resin prepolymer, resorcinol reacts one or both of gained resin prepolymer hybrid resin performed polymer with formaldehyde；It crosses
Cross sulfate, nitrate or the iron chloride or the one or two or more kinds in frerrous chloride that etal molysite is iron；Benzene in performed polymer
The molar ratio of phenol and/or resorcinol and soft template is 20:1-100:1；Phenol and/or resorcinol and transition in performed polymer
The molar ratio of etal molysite is 10:1-60:1；The molar ratio of phenol and/or resorcinol and organic fluorocompound is in performed polymer
0.25:1-4:1。
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| CN108195906B (en) * | 2016-12-08 | 2020-05-05 | 中国科学院大连化学物理研究所 | Molybdenum-nickel composite carbonitride electrocatalytic hydrogen evolution electrode and preparation and application thereof |
| CN107473218B (en) * | 2017-02-13 | 2020-01-07 | 天津城建大学 | Ordered graded porous carbon material with directionally distributed functional groups, preparation method thereof and application thereof in flue gas desulfurization |
| CN108862233A (en) * | 2017-05-10 | 2018-11-23 | 济南圣泉集团股份有限公司 | A kind of graphene composite porous charcoal and its preparation method and application |
| KR102085443B1 (en) * | 2018-09-05 | 2020-03-05 | 인천대학교 산학협력단 | Manufacturing method of nitrogen/fluorine co-doped hollow carbon sphere and its application to supercapacitor |
| CN111326748B (en) * | 2018-12-13 | 2021-11-19 | 中国科学院青岛生物能源与过程研究所 | Transition metal-N/S co-doped porous mulberry-like carbon material catalyst, preparation and application |
| CN110148762B (en) * | 2019-06-26 | 2022-05-31 | 桂林电子科技大学 | Carbon material with nitrogen, fluorine and transition metal co-doped graphene structure and one-step carbonization preparation method thereof |
| CN116422358A (en) * | 2023-04-11 | 2023-07-14 | 湖南大学 | Iron fluorine nitrogen co-doped carbonaceous cathode catalyst and preparation method and application thereof |
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