CN105789569A - Multilevel structure composite material as well as preparation and application thereof - Google Patents
Multilevel structure composite material as well as preparation and application thereof Download PDFInfo
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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
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a multilevel structure composite material. The multilevel structure composite material comprises a macro-porous framework which is composed of graphene and Nafion polyions. The macro-porous framework is loaded with metal nanoparticle nucleating sites; and conducting polymer nano-cluster arrays are in-situ grown at the nucleating sites. The metal nanoparticles are nanoparticles of one of palladium, platinum, gold, silver and iridium or are nanoparticles of an alloy formed by more than two of palladium, platinum, gold, silver and iridium. The conducting polymer is one of polypyrrole, polyaniline, polythiophene and polyacetylene. The composite material has the porosity of 0.5-0.9 and the aperture of 1-10 microns. The conducting polymer nano-cluster array is 10-500 nanometers in diameter and 20-2000 microns in length. The preparation method of the multilevel structure composite material comprises preparation of the macro-porous framework which is loaded with the metal nanoparticle nucleating sites and preparation of the multilevel structure composite material. The multilevel structure composite material has the advantages of high conductivity, simple preparation method, adaptability to large-batch preparation, and the like.
Description
Technical field
The present invention relates to a kind of new multistage composite nano materials, this material has the structure of a kind of big hole on framework specifically, having the secondary structure of nano-array on hole wall, it can be used in the electrodes such as Proton Exchange Membrane Fuel Cells, direct liquid fuel battery, metal-air battery and ultracapacitor.
The preparation method that the invention still further relates to above-mentioned composite.
Background technology
The conductive material with multi-level nano-structure has huge application potential in fields such as electronics, the energy, biological medicines.The allotrope of the rare a kind of carbon as latest find of graphite, the two dimensional crystal structure of its uniqueness imparts the electricity of its excellence, calorifics, mechanical property so that it is become the active material of field of chemical power source.But we are simultaneously it also seen that rare the had lamellar structure of graphite, very easily occur stacking, it is difficult to being effectively realized material transmission, application in the electrodes receives great obstruction.Therefore, the multi-level nano-structure of three dimension scale is set up, it is possible to break through the restriction of its lamellar structure, thus realizing effective application of the rare material of graphite.The conducting polymer materials being representative with polypyrrole, is a kind of new material with matter property and inorganic matter character, has huge application potential in field widely.Generally adopt chemistry from bottom to top or electrochemical method synthesis due to it, its appearance structure can realize effective regulation and control at nanoscale, it is easy to accomplish prepares with the compound of other materials.But the electric conductivity that conducting polymer itself has typically requires external ions carries out doping realization, and electric conductivity is also difficult to reach the level of conventional carbon material or metal material, thus the application in chemical electric power source electrode has been also affected by certain restriction.
In sum, design preparing have the graphite of multi-level nano-structure rare/conducting polymer composite material, it is possible in conjunction with the two advantage and overcome defect each other, it is achieved it, in the application in chemical electric power source electrode field, has important using value.
The present invention utilizes this characteristic of bigger serface of the rare material of graphite, in the electrochemistry nucleation site of its surface preparation growth conducting polymer, and constructs macropore framing structure.Then electrochemical polymerization is adopted, growth in situ polypyrrrole nano array, it is prepared for multistage composite nanostructure.
Summary of the invention
It is an object of the invention to provide a kind of new multistage structural composite material, this material is by ordered big hole array structure and is attached to the orderly conductive polymer nanometer array structure of hole wall surface and forms, this material has the advantage such as high conductivity, bigger serface, can be used as in Proton Exchange Membrane Fuel Cells, lithium ion battery, ultracapacitor.
For achieving the above object, the present invention adopts scheme in detail below to realize:
A kind of multilevel hierarchy composite, constitutes big hole on framework including by Graphene and Nafion polyion, is supported with metal nanoparticle nucleation site on big hole on framework, and on described nucleation site, growth in situ has conductive polymer nanometer cluster array.
Described metal nanoparticle is the nanoparticle of one or more alloys in palladium, platinum, gold, silver, iridium.Noble metal nano particles has good stability in the electrochemical environment of high potential, and the characterization of adsorption of conductive polymer precursor molecule is made its nucleation site that can grow as conducting polymer by it simultaneously.
Described conducting polymer is the one in polypyrrole, polyaniline, polythiophene, polyacetylene.This type of conducting polymer can carry out electrochemical polymerization reaction under aqueous solution electrochemical oxidizing condition, thus realizing the growth of nano-array.
In described composite, 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 described composite is 0.5-0.9, and aperture is 1-10 micron；The diameter of described conductive polymer nanometer cluster array is 10-500 nanometer, and length is 20-2000 micron.
The preparation method of described multilevel hierarchy composite, comprises the following steps,
A () is supported with the preparation of the macropore framework material in metal nanoparticle nucleation site: add graphite oxide, noble metal precursor salt and Nafion polyion solution in water, after mix homogeneously, solvent flashing is 0.5-20% to the solid content of solution, after lyophilization, it is carried out electronation process, the macropore framework material in metal nanoparticle nucleation site must be supported with；
The preparation of (b) multilevel hierarchy composite: add the electrolyte solution containing the little molecule of conductive polymer precursor and pattern directed agents in the buffer solution that pH value range is 2-13, using step (a) gained macropore framework material as working electrode, three-electrode system makes the precursor little molecule electrochemical polymerization of conducting polymer to the big hole on framework of macropore framework material, obtain multilevel hierarchy composite.
The described noble metal precursor salt of step (a) is one or more in Palladous chloride., chloroplatinic acid, iridium chloride, auric chloride, silver nitrate.
The described Nafion polyion solution of step (a) is aqueous solution and/or the aqueous isopropanol of the Nafion polyion of 5-30%.
The concentration of the described graphite oxide of step (a) is 0.1-10mg/mL；The addition of described noble metal precursor salt and the mass ratio of graphite oxide are 0.05-0.8；The addition of described Nafion polyion solution is so that in solution, the mass ratio of Nafion polyion and graphite oxide is 0.05-10.
The temperature of the described solvent flashing of step (a) is 50-80 DEG C；In described freezing dry process, cryogenic temperature is below zero degrees celsius, and drying condition is that 0-600Pa pressure vacuum dries, the triple point pressure of water is 660Pa, when lower than this critical pressure, water only exists with solid-state and gaseous form, thus the dry run of its distillation can be realized；The described electronation of step (a) processes as the one in hydrogen reduction, sodium borohydride reduction, hydrazine hydrate reduction, vacuum-thermal reduction.
The little molecule of the described conductive polymer precursor of step (b) is the one in pyrroles, aniline, thiophene, acetylene；Conductive polymer precursor little molecule concentration in electrolyte solution is 0.01-0.2M.
The described pattern directed agents of step (b) is one or more in paratoluenesulfonic acid sodium salt, p-methyl benzenesulfonic acid, DBSA；Described pattern directed agents concentration in electrolyte solution is 0.01-0.5M.
The described buffer solution of step (b) is preferably the one in dibastic sodium phosphate or sodium dihydrogen phosphate or disodium hydrogen phosphate.
The described electrochemical polymerization process of step (b) is that saturated calomel electrode is as reference electrode, and polymerization current potential relative saturation calomel electrode is 0.6-0.9V, and polymerization time is 10-60 minute, and polymerization temperature is 5-80 degree Celsius using platinized platinum as to electrode.
When described electronation processes as hydrogen reduction, it is specially and freeze drying example is placed in tube furnace, pass into the gaseous mixture of hydrogen that hydrogen content is 1-20% and noble gas, flow velocity is 10-200mL/min, heating rate is 1-10 DEG C/min, and target temperature is 150-350 DEG C, and the recovery time is 1-8h.
Described electronation processes as sodium borohydride reduction or hydrazine hydrate reduction, concretely comprise the following steps in the aqueous solution that freeze drying example is placed in sodium borohydride that concentration is 0.1-10M or hydrazine hydrate, regulating its pH value is reaction 0.2-6h under 10-14,20-80 DEG C of condition, rinses well with deionized water after taking-up.
Described electronation processes as vacuum-thermal reduction, concretely comprises the following steps and is placed in tube furnace by freeze drying example, and vacuum pump evacuation makes in stove that vacuum is less than 0.2kPa, and heating rate is 1-10 DEG C/min, and target temperature is 150-600 DEG C, and the recovery time is 1-8h.
Described multi-polar structure material can be used for Proton Exchange Membrane Fuel Cells or ultracapacitor or lithium ion battery electrode material.
Compared with prior art, the invention have the advantages that
1. electric conductivity is high: the multilevel hierarchy composite adopting the method for the invention to prepare, and has higher electron conduction.
2. electrochemistry specific surface area is big: the multilevel hierarchy composite adopting the method for the invention to prepare, and has higher specific surface area；
3. mass-transfer performance is good: adopt multilevel hierarchy composite prepared by the method for the invention, and owing to its porosity improves, aperture increases, and mass-transfer performance is more excellent；
4. practical: compared to other preparation methoies, the lyophilization method of reducing of this method is quickly and easily, it is not necessary to coating-dry run, and graphite oxide repeatedly is prepared simple, cheap, is suitable to large batch of preparation process.
Accompanying drawing explanation
The preparation process of Fig. 1 multistage composite nano material of the present invention and structural representation.
The electromicroscopic photograph (embodiment 1) of a kind of multistage composite nano material adopting the method for the invention to prepare in diffusion layer substrate of Fig. 2.Can be seen that this composite porous electrode defines regular macropore framing structure, pore size is about 10 μm, and the rare material of graphite of sheet is the main matter constituting framing structure.Further amplify the pattern of this pore structure, it is possible to finding rare for, on the hole wall of substrate, there is orderly polypyrrrole nano array structure at graphite, these nanometer rods average diameter size are about about 20-30nm, and are uniformly distributed on hole wall.
Detailed description of the invention
Below by way of example, the present invention is described in detail, but the present invention is not limited only to following example.
Embodiment 1:
1) preparation of the rare macropore framing structure of graphite
Adopt graphite oxide prepared by Hummers method with concentration for 0.1mgmL-1Concentration ultrasonic disperse in deionized water；Add and account for the Palladous chloride. that graphite oxide mass fraction is 40%, stir after dissolving；Add Nafion polyion aqueous solution or aqueous isopropanol that mass fraction is 10% so that it is be continuously stirred 12h under 0.5,70 DEG C of water bath condition with the mass ratio of graphite oxide；Solvent flashing under 70 DEG C of conditions so that quality solid content is 2%, obtains combination electrode serosity.
Above-mentioned combination electrode serosity is submerged in liquid nitrogen (or being placed in refrigerator) freezing, be subsequently placed in freezer dryer to carry out the lyophilization of 24h；Take out above-mentioned freeze drying example and carry out hydrogen reducing process, pass into hydrogen volume content be 2% hydrogen-argon-mixed, flow velocity is 50mLmin-1, heating rate is 5 DEG C of min-1, target temperature is 250 DEG C, and the recovery time is 4h, obtains being supported with the rare macropore framing structure of graphite in nucleation site.
2) preparation of conductive polymer nanometer linear array structure
Using the above-mentioned rare macropore framing structure of graphite being supported with nucleation site as working electrode, platinized platinum is as to electrode, saturated calomel electrode is as reference electrode, by little for the precursor of conducting polymer molecule electrochemical polymerization to macropore framing structure hole wall surface, containing the little molecule pyrrole concentration of conductive polymer precursor in electrolyte solution is 0.1M, pattern directed agents p-methyl benzenesulfonic acid na concn is 0.1M, buffer solution (phosphate buffer solution) pH value is 6.9, polymerization current potential is 0.65V (relative saturation calomel electrode), polymerization time is 30 minutes, polymerization temperature is 25 degrees Celsius.
Claims (19)
1. a multilevel hierarchy composite, it is characterised in that: including being constituted big hole on framework by Graphene and Nafion polyion, be supported with metal nanoparticle nucleation site on big hole on framework, on described nucleation site, growth in situ has conductive polymer nanometer cluster array.
2. multilevel hierarchy composite as claimed in claim 1, it is characterised in that: described metal nanoparticle is the nanoparticle of one or more alloys in palladium, platinum, gold, silver, iridium.
3. multilevel hierarchy composite as claimed in claim 1, it is characterised in that: described conducting polymer is the one in polypyrrole, polyaniline, polythiophene, polyacetylene.
4. multilevel hierarchy composite as claimed in claim 1, it is characterised in that: in described composite, 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%.
5. multilevel hierarchy composite as claimed in claim 1, it is characterised in that: the porosity of described composite is 0.5-0.9, and aperture is 1-10 micron.
6. multilevel hierarchy composite as claimed in claim 1, it is characterised in that: the diameter of described conductive polymer nanometer cluster array is 10-500 nanometer, and length is 20-2000 micron.
7. the preparation method of the arbitrary described multilevel hierarchy composite of claim 1-6, it is characterised in that: comprise the following steps,
A () is supported with the preparation of the macropore framework material in metal nanoparticle nucleation site: add graphite oxide, noble metal precursor salt and Nafion polyion solution in water, after mix homogeneously, solvent flashing is 0.5-20% to the solid content of solution, after lyophilization, it is carried out electronation process, the macropore framework material in metal nanoparticle nucleation site must be supported with；
The preparation of (b) multilevel hierarchy composite: add the electrolyte solution containing the little molecule of conductive polymer precursor and pattern directed agents in the buffer solution that pH value range is 2-13, using step (a) gained macropore framework material as working electrode, three-electrode system makes the precursor little molecule electrochemical polymerization of conducting polymer to the big hole on framework of macropore framework material, obtain multilevel hierarchy composite.
8. the preparation method of multilevel hierarchy composite as claimed in claim 7, it is characterised in that:
The described noble metal precursor salt of step (a) is one or more in Palladous chloride., chloroplatinic acid, iridium chloride, auric chloride, silver nitrate.
9. the preparation method of multilevel hierarchy composite as claimed in claim 7, it is characterised in that:
The described Nafion polyion solution of step (a) is aqueous solution and/or the aqueous isopropanol of the Nafion polyion of 5-30%.
10. the preparation method of multilevel hierarchy composite as claimed in claim 7, it is characterised in that:
The concentration of the described graphite oxide of step (a) is 0.1-10mg/mL；The addition of described noble metal precursor salt and the mass ratio of graphite oxide are 0.05-0.8；The addition of described Nafion polyion solution is so that in solution, the mass ratio of Nafion polyion and graphite oxide is 0.05-10.
11. the preparation method of multilevel hierarchy composite as claimed in claim 7, it is characterised in that:
The temperature of the described solvent flashing of step (a) is 50-80 DEG C；In described freezing dry process, cryogenic temperature is below zero degrees celsius, and drying condition is that 0-600Pa pressure vacuum dries；The described electronation of step (a) processes as the one in hydrogen reduction, sodium borohydride reduction, hydrazine hydrate reduction, vacuum-thermal reduction.
12. the preparation method of multilevel hierarchy composite as claimed in claim 7, it is characterised in that:
The little molecule of the described conductive polymer precursor of step (b) is the one in pyrroles, aniline, thiophene, acetylene；Conductive polymer precursor little molecule concentration in electrolyte solution is 0.01-0.2M.
13. the preparation method of multilevel hierarchy composite as claimed in claim 7, it is characterised in that:
The described pattern directed agents of step (b) is one or more in paratoluenesulfonic acid sodium salt, p-methyl benzenesulfonic acid, DBSA；Described pattern directed agents concentration in electrolyte solution is 0.01-0.5M.
14. the preparation method of multilevel hierarchy composite as claimed in claim 7, it is characterised in that:
The described buffer solution of step (b) is preferably the one in dibastic sodium phosphate or sodium dihydrogen phosphate or disodium hydrogen phosphate.
15. the preparation method of multilevel hierarchy composite as claimed in claim 7, it is characterised in that:
The described electrochemical polymerization process of step (b) is that saturated calomel electrode is as reference electrode, and polymerization current potential relative saturation calomel electrode is 0.6-0.9V, and polymerization time is 10-60 minute, and polymerization temperature is 5-80 degree Celsius using platinized platinum as to electrode.
16. the preparation method of multilevel hierarchy composite as claimed in claim 11, it is characterised in that:
When described electronation processes as hydrogen reduction, it is specially and freeze drying example is placed in tube furnace, pass into the gaseous mixture of hydrogen that hydrogen content is 1-20% and noble gas, flow velocity is 10-200mL/min, heating rate is 1-10 DEG C/min, and target temperature is 150-350 DEG C, and the recovery time is 1-8h.
17. the preparation method of multilevel hierarchy composite as claimed in claim 11, it is characterised in that:
Described electronation processes as sodium borohydride reduction or hydrazine hydrate reduction, concretely comprise the following steps in the aqueous solution that freeze drying example is placed in sodium borohydride that concentration is 0.1-10M or hydrazine hydrate, regulating its pH value is reaction 0.2-6h under 10-14,20-80 DEG C of condition, rinses well with deionized water after taking-up.
18. the preparation method of multilevel hierarchy composite as claimed in claim 11, it is characterised in that:
Described electronation processes as vacuum-thermal reduction, concretely comprises the following steps and is placed in tube furnace by freeze drying example, and vacuum pump evacuation makes in stove that vacuum is less than 0.2kPa, and heating rate is 1-10 DEG C/min, and target temperature is 150-600 DEG C, and the recovery time is 1-8h.
19. the application of the arbitrary described multilevel hierarchy composite of claim 1-6, it is characterised in that: described multi-polar structure material can be used for Proton Exchange Membrane Fuel Cells or ultracapacitor or lithium ion battery electrode material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108832152A (en) * | 2018-06-26 | 2018-11-16 | 李荣旭 | A kind of band coating proton exchange membrane fuel cell metal flow-field plate |
| CN109923631A (en) * | 2016-09-26 | 2019-06-21 | 加利福尼亚大学董事会 | The method for having hole graphene frame compound and prepare the compound for ultra-high magnifications energy storage |
| 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 |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101286564A (en) * | 2008-05-28 | 2008-10-15 | 中国科学院上海微系统与信息技术研究所 | Composite anode for direct methanol fuel cell and method for making the same |
| CN101474557A (en) * | 2009-01-06 | 2009-07-08 | 上海汽车工业(集团)总公司 | Electrocatalyst support, electrocatalyst and electrode for fuel cell and preparation thereof |
| CN102784665A (en) * | 2012-08-20 | 2012-11-21 | 湖南科技大学 | Carbon, silver-copper and polyaniline composite electro-catalyst for oxygen reduction reaction of fuel cell and preparation method and application of electro-catalyst |
| CN103123974A (en) * | 2011-11-18 | 2013-05-29 | 中国科学院大连化学物理研究所 | Conducting polymer/metal/proton exchange composite membrane and preparation and application thereof |
-
2014
- 2014-12-19 CN CN201410805129.XA patent/CN105789569B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101286564A (en) * | 2008-05-28 | 2008-10-15 | 中国科学院上海微系统与信息技术研究所 | Composite anode for direct methanol fuel cell and method for making the same |
| CN101474557A (en) * | 2009-01-06 | 2009-07-08 | 上海汽车工业(集团)总公司 | Electrocatalyst support, electrocatalyst and electrode for fuel cell and preparation thereof |
| CN103123974A (en) * | 2011-11-18 | 2013-05-29 | 中国科学院大连化学物理研究所 | Conducting polymer/metal/proton exchange composite membrane and preparation and application thereof |
| CN102784665A (en) * | 2012-08-20 | 2012-11-21 | 湖南科技大学 | Carbon, silver-copper and polyaniline composite electro-catalyst for oxygen reduction reaction of fuel cell and preparation method and application of electro-catalyst |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109923631A (en) * | 2016-09-26 | 2019-06-21 | 加利福尼亚大学董事会 | The method for having hole graphene frame compound and prepare the compound for ultra-high magnifications energy storage |
| CN108832152A (en) * | 2018-06-26 | 2018-11-16 | 李荣旭 | A kind of band coating proton exchange membrane fuel cell metal flow-field plate |
| 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 |
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