CN105789569B - A kind of multilevel structure composite material and its preparation and application - Google Patents
A kind of multilevel structure composite material and its preparation and application Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A kind of multilevel structure composite material, including big hole on framework is constituted by graphene and Nafion polyion, in being supported with metal nanoparticle nucleation site on big hole on framework, growth in situ has conductive polymer nanometer cluster array in Yu Suoshu nucleation site.The metal nanoparticle is the nanoparticle of one or more of palladium, platinum, gold, silver, iridium alloy.The conducting polymer is one of polypyrrole, polyaniline, polythiophene, polyacetylene.The porosity of the composite material is 0.5-0.9, and aperture is 1-10 microns.The diameter of the conductive polymer nanometer cluster array is 10-500 nanometers, and length is 20-2000 microns.The preparation method of the multilevel structure composite material, including being supported with the preparation of the macropore framework material of metal nanoparticle nucleation site and the preparation of multilevel structure composite material.The advantages that composite material of the present invention is conductive high, preparation method is simple, suitable for large batch of preparation.
Description
Technical field
The present invention relates to a kind of new multistage composite nano materials, and specifically this material has a kind of big hole on framework
Structure can be used for Proton Exchange Membrane Fuel Cells, direct liquid fuel power with the secondary structure of nano-array on hole wall
In the electrodes such as pond, metal-air battery and supercapacitor.
The invention further relates to the preparation methods of above-mentioned composite material.
Background technique
Conductive material with multi-level nano-structure is latent with huge application in fields such as electronics, the energy, biological medicines
Power.A kind of allotrope of the dilute carbon as latest find of graphite, it is excellent that unique two dimensional crystal structure imparts it
Electricity, calorifics, mechanical property become the active material of field of chemical power source.But we are simultaneously it also seen that graphite is dilute is had
Some lamellar structures, easily stack, it is difficult to effectively realize substance transmitting, application in the electrodes receives great resistance
Hinder.Therefore, the multi-level nano-structure of three dimension scale is established, it is possible to the limitation of its lamellar structure is broken through, to realize that graphite is dilute
Effective application of material.Using polypyrrole as the conducting polymer materials of representative, be it is a kind of and meanwhile have matter property with it is inorganic
The new material of physical property matter has huge application potential in extensive field.Since it generallys use chemistry from bottom to top
Or electrochemical method synthesis, appearance structure can realize effective regulation in nanoscale, it is easy to accomplish with answering for other materials
Close preparation.But electric conductivity possessed by conducting polymer itself usually requires external ions and is doped realization, and electric conductivity is also difficult
Application to reach the level of traditional carbon material or metal material, thus in chemical electric power source electrode also receives certain limit
System.
In conclusion design and prepare the graphite with multi-level nano-structure it is dilute/conducting polymer composite material, it is possible to
In conjunction with the two advantage and overcome mutual defect, realize that it in the application in chemical electric power source electrode field, has important application
Value.
The present invention utilizes this characteristic of the bigger serface of the dilute material of graphite, prepares growth conducting polymer in its surface
Electrochemistry nucleation site, and construct macropore skeleton structure.Then electrochemical polymerization is used, growth in situ polypyrrole is received
Rice array, is prepared for multistage composite nanostructure.
Summary of the invention
The purpose of the present invention is to provide a kind of new multistage structural composite materials, and the material is by ordered big hole array structure
And it is attached to the orderly conductive polymer nanometer array structure composition of hole wall surface, which has high conductivity, compares table greatly
The advantages that area, can be used as Proton Exchange Membrane Fuel Cells, lithium ion battery, in supercapacitor.
To achieve the above object, the present invention is realized using scheme in detail below:
A kind of multilevel structure composite material, including big hole on framework, Yu great Kong bone are constituted by graphene and Nafion polyion
Metal nanoparticle nucleation site is supported on frame, growth in situ has conductive polymer nanometer cluster battle array in Yu Suoshu nucleation site
Column.
The metal nanoparticle is the nanoparticle of one or more of palladium, platinum, gold, silver, iridium alloy.Your gold
It is with good stability in the electrochemical environment of high potential to belong to nanoparticle, while it is to conductive polymer precursor molecule
Characterization of adsorption makes it can be used as the nucleation site of conducting polymer growth.
The conducting polymer is one of polypyrrole, polyaniline, polythiophene, polyacetylene.Such conducting polymer can
Electrochemical polymerization reaction is carried out under aqueous solution electrochemical oxidizing condition, to realize the growth of nano-array.
In the composite material, the mass content of graphene is 20-75%；The mass content of Nafion polyion is 15-
50%；The mass content of conducting polymer is 5-50%；The mass content of metal nanoparticle is 5-30%.
The porosity of the composite material is 0.5-0.9, and aperture is 1-10 microns；The conductive polymer nanometer cluster array
Diameter be 10-500 nanometer, length be 20-2000 microns.
The preparation method of the multilevel structure composite material, includes the following steps,
(a) be supported with the preparation of the macropore framework material of metal nanoparticle nucleation site: in water be added graphite oxide,
Noble metal precursor salt and Nafion polyion solution, the solid content of solvent flashing to solution is 0.5-20% after mixing, cold
Be lyophilized it is dry after electronation processing is carried out to it, the macropore framework material of metal nanoparticle nucleation site must be supported with；
(b) it the preparation of multilevel structure composite material: is added in the buffer solution that pH value range is 2-13 containing conductive poly-
The electrolyte solution of polymer precursor small molecule and pattern directed agents, using macropore framework material obtained by step (a) as working electrode,
Make to obtain in the precursor small molecule electrochemical polymerization of conducting polymer to the big hole on framework of macropore framework material in three-electrode system
Multilevel structure composite material.
Step (a) the noble metal precursor salt be one of palladium chloride, chloroplatinic acid, iridium chloride, chlorauride, silver nitrate or
It is two or more.
Step (a) the Nafion polyion solution is the aqueous solution and/or isopropanol of the Nafion polyion of 5-30%
Solution.
The concentration of step (a) graphite oxide is 0.1-10mg/mL；The additional amount and oxidation of the noble metal precursor salt
The mass ratio of graphite is 0.05-0.8；The additional amount of the Nafion polyion solution be so that in solution Nafion polyion with
The mass ratio of graphite oxide is 0.05-10.
The temperature of step (a) solvent flashing is 50-80 DEG C；In the freezing dry process, cryogenic temperature is zero to take the photograph
Family name's degree is hereinafter, drying condition is dry for 0-600Pa pressure vacuum, and the triple point pressure of water is 660Pa, when lower than this critical pressure
When, water only exists with solid-state and gaseous form, so that the drying process of its distillation can be realized；At step (a) electronation
Reason is one of hydrogen reduction, sodium borohydride reduction, hydrazine hydrate reduction, vacuum-thermal reduction.
Step (b) the conductive polymer precursor small molecule is one of pyrroles, aniline, thiophene, acetylene；Conducting polymer
Concentration of the object precursor small molecule in electrolyte solution is 0.01-0.2M.
Step (b) the pattern directed agents are one of paratoluenesulfonic acid sodium salt, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid
Or it is two or more；Concentration of the pattern directed agents in electrolyte solution is 0.01-0.5M.
Step (b) buffer solution is preferably dibastic sodium phosphate or one of sodium dihydrogen phosphate or disodium hydrogen phosphate.
Step (b) electrochemical polymerization process be using platinized platinum as to electrode, saturated calomel electrode as reference electrode,
Polymerization current potential relative saturation calomel electrode is 0.6-0.9V, and polymerization time is 10-60 minutes, and polymerization temperature is 5-80 degrees Celsius.
When the electronation processing is hydrogen reduction, specially freeze drying example is placed in tube furnace, is passed through hydrogen
Content is the hydrogen of 1-20% and the gaseous mixture of inert gas, and flow velocity 10-200mL/min, heating rate is 1-10 DEG C/min,
Target temperature is 150-350 DEG C, recovery time 1-8h.
The electronation processing is sodium borohydride reduction or hydrazine hydrate reduction, and the specific steps are set freeze drying example
In the aqueous solution of sodium borohydride or hydrazine hydrate that concentration is 0.1-10M, its pH value is adjusted for 10-14, under the conditions of 20-80 DEG C instead
0.2-6h is answered, is rinsed well after taking-up with deionized water.
The electronation processing is vacuum-thermal reduction, the specific steps are freeze drying example to be placed in tube furnace, very
Empty pumping vacuum makes vacuum degree in furnace be less than 0.2kPa, and heating rate is 1-10 DEG C/min, and target temperature is 150-600 DEG C,
Recovery time is 1-8h.
The multi-polar structure material can be used for Proton Exchange Membrane Fuel Cells or supercapacitor or lithium ion battery battery
Pole material.
Compared with prior art, the invention has the following advantages that
1. electric conductivity is high: the multilevel structure composite material prepared using the method for the invention, electronics with higher are led
Electrically.
2. electrochemistry large specific surface area: the multilevel structure composite material prepared using the method for the invention is had higher
Specific surface area；
3. mass-transfer performance is good: the multilevel structure composite material prepared using the method for the invention, since its porosity mentions
Height, aperture increases, mass-transfer performance are more excellent；
4. practical: compared to other preparation methods, the freeze-drying restoring method of this method is quick and easy, without anti-
- drying process is covered in overcoating, and graphite oxide prepares simple, cheap, is suitable for large batch of preparation process.
Detailed description of the invention
The preparation process and structural schematic diagram of Fig. 1 multistage composite nano material of the present invention.
A kind of Electronic Speculum of multistage composite nano material prepared in diffusion layer substrate using the method for the invention of Fig. 2 is shone
Piece (embodiment 1).It can be seen that this composite porous electrode forms regular macropore skeleton structure, pore size is about 10
μm, the dilute material of the graphite of sheet is the main matter for constituting skeleton structure.Further amplify the pattern of this pore structure, it can be with
It was found that, there are orderly polypyrrrole nano array structure, these nanometer rods average diameters are big on the dilute hole wall for substrate of graphite
Small about 20-30nm or so, and be uniformly distributed on hole wall.
Specific embodiment
Below by way of example, the present invention is described in detail, but the present invention is not limited only to following embodiment.
Embodiment 1:
1) preparation of the dilute macropore skeleton structure of graphite
The graphite oxide for using Hummers method to prepare is with concentration for 0.1mg mL-1Concentration ultrasonic disperse in deionized water
In；It is added and accounts for the palladium chloride that graphite oxide mass fraction is 40%, stirred evenly after dissolution；It is 10% that mass fraction, which is added,
Nafion polyion aqueous solution or aqueous isopropanol make to hold under its 0.5,70 DEG C of water bath condition of mass ratio with graphite oxide
Continuous stirring 12h；Solvent flashing under the conditions of 70 DEG C obtains combination electrode slurries so that quality solid content is 2%.
Above-mentioned combination electrode slurries are submerged into liquid nitrogen (or being placed in refrigerator) freezing, are subsequently placed in freeze drier
Carry out freeze-drying for 24 hours；It takes out above-mentioned freeze drying example and carries out hydrogen reducing processing, being passed through hydrogen volume content is 2%
It is hydrogen-argon-mixed, flow velocity be 50mL min-1, heating rate is 5 DEG C of min-1, target temperature is 250 DEG C, and the recovery time is
4h obtains the dilute macropore skeleton structure of graphite for being supported with nucleation site.
2) preparation of conductive polymer nanometer linear array structure
Using the dilute macropore skeleton structure of the above-mentioned graphite for being supported with nucleation site as working electrode, platinized platinum is used as to electrode,
Saturated calomel electrode is as reference electrode, by the precursor small molecule electrochemical polymerization of conducting polymer to macropore skeleton structure hole wall
Surface containing conductive polymer precursor small molecule pyrrole concentrations is 0.1M, pattern directed agents p-methyl benzenesulfonic acid in electrolyte solution
Na concn is 0.1M, and buffer solution (phosphate buffer solution) pH value is 6.9, and polymerization current potential is 0.65V (relative saturation calomel electricity
Pole), polymerization time is 30 minutes, and polymerization temperature is 25 degrees Celsius.
Claims (19)
1. a kind of multilevel structure electrode material, it is characterised in that: including constituting big hole on framework by graphene and Nafion polyion,
In being supported with metal nanoparticle nucleation site on big hole on framework, growth in situ has conducting polymer to receive in Yu Suoshu nucleation site
Rice cluster array.
2. multilevel structure electrode material as described in claim 1, it is characterised in that: the metal nanoparticle be palladium, platinum, gold,
The nanoparticle of one or more of silver, iridium alloy.
3. multilevel structure electrode material as described in claim 1, it is characterised in that: the conducting polymer is polypyrrole, polyphenyl
One of amine, polythiophene, polyacetylene.
4. multilevel structure electrode material as described in claim 1, it is characterised in that: in the multilevel structure electrode material, graphite
The mass content of alkene is 20-75%；The mass content of Nafion polyion is 15-50%；The mass content of conducting polymer is 5-
50%；The mass content of metal nanoparticle is 5-30%.
5. multilevel structure electrode material as described in claim 1, it is characterised in that: the porosity of the multilevel structure electrode material
For 0.5-0.9, aperture is 1-10 microns.
6. multilevel structure electrode material as described in claim 1, it is characterised in that: the conductive polymer nanometer cluster array it is straight
Diameter is 10-500 nanometers, and length is 20-2000 microns.
7. a kind of preparation method of any multilevel structure electrode material of claim 1-6, it is characterised in that: including following step
Suddenly,
(a) it is supported with the preparation of the macropore framework material of metal nanoparticle nucleation site: graphite oxide, expensive being added in water
Metal precursor salts and Nafion polyion solution, the solid content of solvent flashing to solution is 0.5-20% after mixing, and freezing is dry
Electronation processing is carried out to it after dry, the macropore framework material of metal nanoparticle nucleation site must be supported with；
(b) it the preparation of multilevel structure electrode material: is added in the buffer solution that pH value range is 2-13 and contains conducting polymer
The electrolyte solution of precursor small molecule and pattern directed agents, using macropore framework material obtained by step (a) as working electrode, three
Make to obtain multistage in the precursor small molecule electrochemical polymerization of conducting polymer to the big hole on framework of macropore framework material in electrode system
Structure electrode material.
8. the preparation method of multilevel structure electrode material as claimed in claim 7, it is characterised in that:
Step (a) the noble metal precursor salt is one or both of palladium chloride, chloroplatinic acid, iridium chloride, chlorauride, silver nitrate
More than.
9. the preparation method of multilevel structure electrode material as claimed in claim 7, it is characterised in that:
Step (a) the Nafion polyion solution is the aqueous solution and/or aqueous isopropanol of the Nafion polyion of 5-30%.
10. the preparation method of multilevel structure electrode material as claimed in claim 7, it is characterised in that:
The concentration of step (a) graphite oxide is 0.1-10 mg/mL；The additional amount and oxidation stone of the noble metal precursor salt
The mass ratio of ink is 0.05-0.8；The additional amount of the Nafion polyion solution is so that Nafion polyion and oxygen in solution
The mass ratio of graphite is 0.05-10.
11. the preparation method of multilevel structure electrode material as claimed in claim 7, it is characterised in that:
The temperature of step (a) solvent flashing is 50-80 DEG C；In the freezing dry process, cryogenic temperature is zero degrees celsius
Hereinafter, drying condition is dry for 0-600 Pa pressure vacuum；Step (a) the electronation processing is hydrogen reduction, sodium borohydride
One of reduction, hydrazine hydrate reduction, vacuum-thermal reduction.
12. the preparation method of multilevel structure electrode material as claimed in claim 7, it is characterised in that:
Step (b) the conductive polymer precursor small molecule is one of pyrroles, aniline, thiophene, acetylene；Before conducting polymer
Concentration of the body small molecule in electrolyte solution is 0.01-0.2M.
13. the preparation method of multilevel structure electrode material as claimed in claim 7, it is characterised in that:
Step (b) the pattern directed agents are one of paratoluenesulfonic acid sodium salt, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid or two
Kind or more；Concentration of the pattern directed agents in electrolyte solution is 0.01-0.5M.
14. the preparation method of multilevel structure electrode material as claimed in claim 7, it is characterised in that:
Step (b) buffer solution is preferably dibastic sodium phosphate or one of sodium dihydrogen phosphate or disodium hydrogen phosphate.
15. the preparation method of multilevel structure electrode material as claimed in claim 7, it is characterised in that:
Step (b) electrochemical polymerization process is using platinized platinum as to electrode, and saturated calomel electrode is as reference electrode, polymerization
Current potential relative saturation calomel electrode is 0.6-0.9 V, and polymerization time is 10-60 minutes, and polymerization temperature is 5-80 degrees Celsius.
16. the preparation method of multilevel structure electrode material as claimed in claim 11, it is characterised in that:
When the electronation processing is hydrogen reduction, specially freeze drying example is placed in tube furnace, is passed through hydrogen content
For the hydrogen of 1-20% and the gaseous mixture of inert gas, flow velocity is 10-200 mL/min, heating rate 1-10oC/min, mesh
Mark temperature is 150-350oC, recovery time are 1-8 h.
17. the preparation method of multilevel structure electrode material as claimed in claim 11, it is characterised in that:
Electronation processing is sodium borohydride reduction or hydrazine hydrate reduction, dense the specific steps are freeze drying example to be placed in
Degree is in the sodium borohydride of 0.1-10 M or the aqueous solution of hydrazine hydrate, and adjusting its pH value is 10-14,20-80oIt is reacted under the conditions of C
0.2-6h is rinsed well after taking-up with deionized water.
18. the preparation method of multilevel structure electrode material as claimed in claim 11, it is characterised in that:
Electronation processing is vacuum-thermal reduction, the specific steps are freeze drying example is placed in tube furnace, vacuum pump
It vacuumizes so that vacuum degree is less than 0.2 kPa, heating rate 1-10 in furnaceoC/min, target temperature 150-600oC, also
The former time is 1-8 h.
19. a kind of application of any multilevel structure electrode material of claim 1-6, it is characterised in that: the multilevel structure
Material is for Proton Exchange Membrane Fuel Cells or supercapacitor or lithium ion battery electrode material.
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| CN106098408A (en) * | 2016-07-31 | 2016-11-09 | 肖丽芳 | A kind of preparation method of lithium ion super capacitor grapheme composite positive electrode material |
| CN106129460A (en) * | 2016-08-24 | 2016-11-16 | 宁波嘉宁电池科技有限责任公司 | A kind of multicomponent material combination electrode and lithium ion battery thereof |
| TWI780072B (en) * | 2016-09-26 | 2022-10-11 | 加州大學董事會 | Holey graphene framework composites for ultra-high rate energy storage and methods of preparing such composites |
| CN108832152B (en) * | 2018-06-26 | 2020-11-24 | 山东亚泰新材料科技有限公司 | Coated metal flow field plate of proton exchange membrane fuel cell |
| CN111349338A (en) * | 2018-12-21 | 2020-06-30 | 中国科学院大连化学物理研究所 | Lamellar array composite material for heat absorption and conduction and preparation and application thereof |
| CN109950554A (en) * | 2019-01-09 | 2019-06-28 | 柯良节 | A kind of graphene-supported metal nano island catalyst and the preparation method and application thereof |
| CN115839031A (en) * | 2022-11-25 | 2023-03-24 | 中国科学院大连化学物理研究所 | Ordered conductive polymer composite material and preparation method and application thereof |
| CN118073544B (en) * | 2024-02-19 | 2024-08-16 | 东莞市东美石墨实业有限公司 | High-power graphite electrode and preparation method thereof |
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