CN108281675A - A kind of hollow ball shape carbonitride wraps up copper-based fuel-cell catalyst and preparation method - Google Patents
A kind of hollow ball shape carbonitride wraps up copper-based fuel-cell catalyst and preparation method Download PDFInfo
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- H01M4/00—Electrodes
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- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
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Abstract
The present invention relates to the preparation field of fuel-cell catalyst, discloses a kind of hollow ball shape carbonitride and wrap up copper-based fuel-cell catalyst and preparation method.Including following preparation process：（1）Copper powder is added in melamine and carbon tetrachloride, carries out solvent thermal reaction, the copper colloid of globular graphite phase carbon nitride package is made；（2）Pore creating material and binder will be added in colloid obtained, row heat-treatment of annealing wraps up copper-based fuel-cell catalyst to get hollow ball shape carbonitride after being coated on electrode, and each component parts by weight are：93 ~ 96 parts of colloid, 3 ~ 5 parts of pore creating material, 1 ~ 2 part of binder.Fuel-cell catalyst produced by the present invention is compared with commonly nitridation carbons catalyst, it is compound with carbonitride to cross copper/copper oxide particle, catalytic activity is good, mechanical property and processing performance are good, performance is stablized, porous structure is formd, large specific surface area has fabulous application prospect in Proton Exchange Membrane Fuel Cells.
Description
Technical field
The present invention relates to the preparation fields of fuel-cell catalyst, disclose a kind of copper-based combustion of hollow ball shape carbonitride package
Expect cell catalyst and preparation method.
Background technology
Proton Exchange Membrane Fuel Cells is hydrogen and oxygen using proton exchange membrane as electrolyte（Or air）It is the one of fuel
Kind by the chemical energy being stored in fuel and oxidant be directly translated into electric energy power generator it relative to other fuel cells,
With high efficiency, start many advantages, such as fast, operating temperature is low, pollution-free, is applied to electric vehicle, Portable power generation device
Deng having bright prospects, the attention of more and more countries and enterprise are caused, even more growth momentum is swift and violent in recent years.
Catalyst is one of critical material in fuel cell, and the cost of catalyst accounts for the 1/3 of fuel cell cost.Platinum
Be proved to be the optimum catalyst active component for low-temperature fuel cell, but use platinum as fuel-cell catalyst there is also
Following serious problems：Platinum scarcity of resources；It is expensive；Poison resistance is poor.Have at present come the research for improving catalyst by alloy
The platinum-ruthenium alloys catalyst of carbon load, and Pt/C the and PtRu/C catalyst etc. added with other promotion ingredients.Therefore
Develop the research ever more important of non-platinum or low-platinum catalyst.
In the research of non-platinum catalyst, nitrogen-doped carbon material is paid attention to by researcher, but traditional technology still can not be complete
The dependence that complete solution is determined for platinum-base material.Hollow sphere carbonitride is due to its structure problem, during being catalyzed use easily
There are structure collapses, the catalytic performance and stable structure Journal of Sex Research to form carbon distribution, therefore for non-platinum catalyst have ten
Divide important practical significance.
Chinese invention patent application number 201310606627.7 discloses a kind of metal/class graphitic nitralloy carbon（g-C3N4）It is multiple
Mixture catalyst and preparation method thereof.The chemical composition for metal/class graphitic nitralloy carbon that the invention provides is M/g-C3N4, wherein
Metal M is Au, Ag, Pt, Pd, Bi, Cu, Ru or Rh, and the content of metal is 0~50%（Mass fraction）.Metal/class graphitic nitralloy
Carbon complex is suitable for restoring nitrobenzene derivative as the catalytic reducer under normal temperature and pressure.
Chinese invention patent application number 201310303367.6 discloses a kind of high graphitization for fuel battery negative pole
The preparation method for spending carbon base catalyst after presoma high-temperature heating melting, immerses template using pitch as carbon precursor；
After stirring evenly, nitrogenous precursor is added thereto, while adding metal salt；Then through drying, high-temperature process and secondary nitridation；
It then washs in an acidic solution, removes template；Finally through being filtered, washed and dried the dry N doping for finally obtaining high graphitization degree
Carbon base catalyst material；The catalyst has high graphitization degree, high-specific surface area and orderly pore structure.It is used as proton exchange membrane
When fuel battery cathod catalyst, good oxygen reduction activity is shown, and the catalyst is environmental-friendly, at low cost, microcosmic
Controllably, resourceful, promise to be the elctro-catalyst of Proton Exchange Membrane Fuel Cells.
According to above-mentioned, in existing scheme platinum base photochemical catalyst there are scarcity of resources, expensive, poison resistance is poor etc. asks
Topic, and traditional platinum base class noble metal catalyst is larger to dependence, specific surface area is small, mechanics and poor processability, graphite-phase
The stability of carbonitride hollow-core construction is poor.
Invention content
At present the wider platinum base photochemical catalyst of application there are scarcity of resources, it is expensive, poison resistance is poor the problems such as, and pass
The problems such as that there are catalyst is larger to dependence for the platinum base class noble metal of system, and specific surface area is small, mechanics and poor processability, graphite
The stability of phase carbon nitride hollow-core construction is poor, limits its development and application, and the present invention proposes a kind of hollow ball shape carbonitride package
Copper-based fuel-cell catalyst and preparation method can effectively solve above-mentioned technical problem.
To solve the above problems, the present invention uses following technical scheme：
A kind of hollow ball shape carbonitride wraps up the preparation method of copper-based fuel-cell catalyst, and the detailed process of preparation is：
（1）Using melamine and carbon tetrachloride as raw material, copper nanoparticle or nano oxidized copper powder is added as template,
Solvent thermal reaction is carried out under 30 ~ 40 DEG C of temperature, the pressure of 15 ~ 20MPa, stops reaction after 40 ~ 50min, globular graphite is made
Copper/copper oxide colloid of phase carbon nitride package；
（2）In step（1）Pore creating material and binder are added in colloid obtained, is uniformly mixed, is then coated on electrode, then set
Heat-treatment of annealing is carried out in vacuum environment, nitride porous carbon coating copper-based catalysts are made, i.e. hollow ball shape carbonitride wraps up
Copper-based fuel-cell catalyst.
Preferably, step（1）The grain size of the copper nanoparticle is 10 ~ 30nm.
Preferably, step（1）Raw material in, in parts by weight, wherein：40 ~ 45 parts of melamine, carbon tetrachloride 47 ~ 56
Part, 4 ~ 8 parts of copper nanoparticle.
Preferably, step（2）The pore creating material is ammonium hydrogen carbonate, azodiisobutyronitrile, bis- benzene disulfohydrazides of 4,4-, 1,3-
At least one of benzene disulfohydrazide.
Preferably, step（2）The binder is in silicone sealants, polyurethane adhesive, epoxy adhesive
At least one.
Preferably, step（2）Raw material in, in parts by weight, wherein：93 ~ 96 parts of colloid, 3 ~ 5 parts of pore creating material, binder
1 ~ 2 part.
Preferably, step（2）The coating thickness is 300 ~ 500 μm.
Preferably, step（2）The temperature of the heat treatment is 800 ~ 1000 DEG C, and soaking time is 100 ~ 120min.
Copper-based fuel-cell catalyst, copper/oxidation are wrapped up by a kind of hollow ball shape carbonitride that the above method is prepared
While copper particle and carbonitride compound holdings oxygen solution catalytic activity, the mechanical property of hollow nitridation carbon ball can be improved and added
Work intensity forms porous structure by vacuum heat, the specific surface area of catalyst is improved, to improve its catalytic performance.This
Method solves traditional catalyst and had been catalyzed to the dependence and graphite phase carbon nitride hollow-core construction of platinum base class precious metal material
Unstable problem in journey.
Compression strength, structural stability and the specific surface area of fuel-cell catalyst prepared by the test present invention, and and stone
Black phase carbon nitride catalyst and platinum base carbon nitride catalyst compare, and method of the invention has a clear superiority, as shown in table 1.
Table 1：
| Performance indicator | The present invention | Graphite phase carbon nitride catalyst | Platinum base carbon nitride catalyst |
| Compression strength（MPa） | 100~160 | 50~100 | 20~80 |
| Structural stability | Without phenomenon of caving in | There is phenomenon of caving in | There is phenomenon of caving in |
| Specific surface area（m2/g) | 300~350 | 220~270 | 180~240 |
The present invention provides a kind of hollow ball shape carbonitrides to wrap up copper-based fuel-cell catalyst and preparation method, with the prior art
It compares, the feature and excellent effect protruded is：
1, it proposes and the copper-based fuel-cell catalyst of hollow ball shape carbonitride package is prepared using melamine and carbon tetrachloride
Method.
2, compound by copper/copper oxide particle and carbonitride in preparing, oxygen solution catalytic activity can be effectively kept, and improve
The mechanical property and processing intensity of hollow nitridation carbon ball, solve the problems, such as that it is unstable in catalytic process.
3, by vacuum heat, form porous structure, significantly improve can catalyst specific surface area, to improve it
Catalytic performance has fabulous application prospect in Proton Exchange Membrane Fuel Cells.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）Using melamine and carbon tetrachloride as raw material, copper nanoparticle is added as template, 35 DEG C of temperature,
Solvent thermal reaction is carried out under the pressure of 18MPa, stops reaction after 45min, and the copper of hollow ball-shape graphite phase carbon nitride package is made
Colloid；The average grain diameter of copper nanoparticle is 20nm；
In parts by weight, wherein：43 parts of melamine, 51 parts of carbon tetrachloride, 6 parts of copper nanoparticle；
（2）In step（1）Pore creating material and binder are added in colloid obtained, is uniformly mixed, is then coated on electrode, then set
Heat-treatment of annealing is carried out in vacuum environment, nitride porous carbon coating copper-based catalysts are made, i.e. hollow ball shape carbonitride wraps up
Copper-based fuel-cell catalyst；Pore creating material is ammonium hydrogen carbonate；Binder is silicone sealants；Average coating thickness is 400 μm；
The temperature of heat treatment is 900 DEG C, soaking time 110min；
In parts by weight, wherein：5 parts of colloid, 4 parts of pore creating material, 1 part of binder.
Hollow ball shape carbonitride made from embodiment 1 wraps up copper-based fuel-cell catalyst, compression strength, stable structure
Property and specific surface area are as shown in table 2.
Embodiment 2
（1）Using melamine and carbon tetrachloride as raw material, copper nanoparticle is added as template, 30 DEG C of temperature,
Solvent thermal reaction is carried out under the pressure of 15MPa, stops reaction after 50min, and the copper of hollow ball-shape graphite phase carbon nitride package is made
Colloid；The average grain diameter of copper nanoparticle is 10nm；
In parts by weight, wherein：40 parts of melamine, 56 parts of carbon tetrachloride, 4 parts of copper nanoparticle；
（2）In step（1）Pore creating material and binder are added in colloid obtained, is uniformly mixed, is then coated on electrode, then set
Heat-treatment of annealing is carried out in vacuum environment, nitride porous carbon coating copper-based catalysts are made, i.e. hollow ball shape carbonitride wraps up
Copper-based fuel-cell catalyst；Pore creating material is azodiisobutyronitrile；Binder is polyurethane adhesive；Average coating thickness is
300μm；The temperature of heat treatment is 800 DEG C, soaking time 120min；
In parts by weight, wherein：96 parts of colloid, 3 parts of pore creating material, 1 part of binder.
Hollow ball shape carbonitride made from embodiment 2 wraps up copper-based fuel-cell catalyst, compression strength, stable structure
Property and specific surface area are as shown in table 2.
Embodiment 3
（1）Using melamine and carbon tetrachloride as raw material, copper nanoparticle is added as template, 40 DEG C of temperature,
Solvent thermal reaction is carried out under the pressure of 20MPa, stops reaction after 40min, and the copper of hollow ball-shape graphite phase carbon nitride package is made
Colloid；The average grain diameter of copper nanoparticle is 30nm；
In parts by weight, wherein：45 parts of melamine, 47 parts of carbon tetrachloride, 8 parts of copper nanoparticle；
（2）In step（1）Pore creating material and binder are added in colloid obtained, is uniformly mixed, is then coated on electrode, then set
Heat-treatment of annealing is carried out in vacuum environment, nitride porous carbon coating copper-based catalysts are made, i.e. hollow ball shape carbonitride wraps up
Copper-based fuel-cell catalyst；Pore creating material is bis- benzene disulfohydrazides of 4,4-；Binder is epoxy adhesive；Average coating is thick
Degree is 500 μm；The temperature of heat treatment is 1000 DEG C, soaking time 100min；
In parts by weight, wherein：93 parts of colloid, 5 parts of pore creating material, 2 parts of binder.
Hollow ball shape carbonitride made from embodiment 3 wraps up copper-based fuel-cell catalyst, compression strength, stable structure
Property and specific surface area are as shown in table 2.
Embodiment 4
（1）Using melamine and carbon tetrachloride as raw material, nano oxidized copper powder is added as template, in 32 DEG C of temperature
It spends, carry out solvent thermal reaction under the pressure of 16MPa, stop reaction after 48min, hollow ball-shape graphite phase carbon nitride package is made
Copper oxide colloid；The average grain diameter of nano oxidized copper powder is 15nm；
In parts by weight, wherein：42 parts of melamine, 53 parts of carbon tetrachloride, 5 parts of copper nanoparticle；
（2）In step（1）Pore creating material and binder are added in colloid obtained, is uniformly mixed, is then coated on electrode, then set
Heat-treatment of annealing is carried out in vacuum environment, nitride porous carbon coating copper-based catalysts are made, i.e. hollow ball shape carbonitride wraps up
Copper-based fuel-cell catalyst；Pore creating material is benzen 1,3 disulphonyl hydrazide；Binder is silicone sealants；Average coating thickness is
350μm；The temperature of heat treatment is 85 DEG C, soaking time 115min；
In parts by weight, wherein：95 parts of colloid, 3 parts of pore creating material, 2 parts of binder.
Hollow ball shape carbonitride made from embodiment 4 wraps up copper-based fuel-cell catalyst, compression strength, stable structure
Property and specific surface area are as shown in table 2.
Embodiment 5
（1）Using melamine and carbon tetrachloride as raw material, copper nanoparticle is added as template, 38 DEG C of temperature,
Solvent thermal reaction is carried out under the pressure of 16MPa, stops reaction after 42min, and the copper of hollow ball-shape graphite phase carbon nitride package is made
Colloid；The average grain diameter of copper nanoparticle is 25nm；
In parts by weight, wherein：44 parts of melamine, 49 parts of carbon tetrachloride, 7 parts of copper nanoparticle；
（2）In step（1）Pore creating material and binder are added in colloid obtained, is uniformly mixed, is then coated on electrode, then set
Heat-treatment of annealing is carried out in vacuum environment, nitride porous carbon coating copper-based catalysts are made, i.e. hollow ball shape carbonitride wraps up
Copper-based fuel-cell catalyst；Pore creating material is ammonium hydrogen carbonate；Binder is polyurethane adhesive；Average coating thickness is 450 μm；
The temperature of heat treatment is 950 DEG C, soaking time 115min；
In parts by weight, wherein：94 parts of colloid, 5 parts of pore creating material, 1 part of binder.
Hollow ball shape carbonitride made from embodiment 5 wraps up copper-based fuel-cell catalyst, compression strength, stable structure
Property and specific surface area are as shown in table 2.
Embodiment 6
（1）Using melamine and carbon tetrachloride as raw material, nano oxidized copper powder is added as template, in 36 DEG C of temperature
It spends, carry out solvent thermal reaction under the pressure of 18MPa, stop reaction after 47min, hollow ball-shape graphite phase carbon nitride package is made
Copper oxide colloid；The average grain diameter of nano oxidized copper powder is 22nm；
In parts by weight, wherein：43 parts of melamine, 52 parts of carbon tetrachloride, 5 parts of copper nanoparticle；
（2）In step（1）Pore creating material and binder are added in colloid obtained, is uniformly mixed, is then coated on electrode, then set
Heat-treatment of annealing is carried out in vacuum environment, nitride porous carbon coating copper-based catalysts are made, i.e. hollow ball shape carbonitride wraps up
Copper-based fuel-cell catalyst；Pore creating material is azodiisobutyronitrile；Binder is epoxy adhesive；Average coating thickness is
420μm；The temperature of heat treatment is 930 DEG C, soaking time 115min；
In parts by weight, wherein：94 parts of colloid, 4 parts of pore creating material, 2 parts of binder.
Hollow ball shape carbonitride made from embodiment 6 wraps up copper-based fuel-cell catalyst, compression strength, stable structure
Property and specific surface area are as shown in table 2.
Comparative example 1
（1）Using melamine and carbon tetrachloride as raw material, copper nanoparticle is added as template, 36 DEG C of temperature,
Solvent thermal reaction is carried out under the pressure of 18MPa, stops reaction after 47min, and the copper of hollow ball-shape graphite phase carbon nitride package is made
Colloid；The average grain diameter of copper nanoparticle is 22nm；
In parts by weight, wherein：43 parts of melamine, 52 parts of carbon tetrachloride, 5 parts of copper nanoparticle；
（2）By step（1）Colloid obtained is coated on electrode, and carbonitride is made and wraps up copper-based fuel-cell catalyst；It is average
Coating thickness is 420 μm.
Pore creating material and binder are added not in colloid for comparative example 1, do not carry out heat-treatment of annealing, and fuel cell obtained is urged
Agent, compression strength, structural stability and specific surface area are as shown in table 2.
The test method of above-mentioned performance indicator is：
The compression strength of catalyst obtained is measured using compression Strength testing machine, compression strength value is obtained, characterizes it
Mechanical property and processing intensity；
Catalyst obtained is used for Catalysis experiments, its structure is observed and whether caves in the generation of phenomenon and carbon distribution, characterize structure
Stability；
The specific surface area of catalyst obtained is measured using specific surface area measuring instrument, obtains specific surface area.
Table 2：
| Performance indicator | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| Compression strength（MPa） | 159 | 156 | 137 | 158 | 149 | 128 | 105 |
| Structural stability | Without phenomenon of caving in | Without phenomenon of caving in | Without phenomenon of caving in | Without phenomenon of caving in | Without phenomenon of caving in | Without phenomenon of caving in | There is phenomenon of caving in |
| Specific surface area（m2/g) | 343 | 326 | 354 | 344 | 338 | 346 | 202 |
Claims (9)
1. a kind of hollow ball shape carbonitride wraps up the preparation method of copper-based fuel-cell catalyst, which is characterized in that the tool of preparation
Body process is：
（1）Using melamine and carbon tetrachloride as raw material, copper nanoparticle or nano oxidized copper powder is added as template,
Solvent thermal reaction is carried out under 30 ~ 40 DEG C of temperature, the pressure of 15 ~ 20MPa, stops reaction after 40 ~ 50min, globular graphite is made
Copper/copper oxide colloid of phase carbon nitride package；
（2）In step（1）Pore creating material and binder are added in colloid obtained, is uniformly mixed, is then coated on electrode, then set
Heat-treatment of annealing is carried out in vacuum environment, nitride porous carbon coating copper-based catalysts are made, i.e. hollow ball shape carbonitride wraps up
Copper-based fuel-cell catalyst.
2. a kind of hollow ball shape carbonitride wraps up the preparation method of copper-based fuel-cell catalyst according to claim 1,
It is characterized in that：Step（1）The grain size of the copper nanoparticle is 10 ~ 30nm.
3. a kind of hollow ball shape carbonitride wraps up the preparation method of copper-based fuel-cell catalyst according to claim 1,
It is characterized in that：Step（1）Raw material in, in parts by weight, wherein：40 ~ 45 parts of melamine, carbon tetrachloride 47 ~ 56 part, nanometer
4 ~ 8 parts of copper powder.
4. a kind of hollow ball shape carbonitride wraps up the preparation method of copper-based fuel-cell catalyst according to claim 1,
It is characterized in that：Step（2）The pore creating material is ammonium hydrogen carbonate, azodiisobutyronitrile, bis- benzene disulfohydrazides of 4,4-, two sulphur of 1,3- benzene
At least one of hydrazides.
5. a kind of hollow ball shape carbonitride wraps up the preparation method of copper-based fuel-cell catalyst according to claim 1,
It is characterized in that：Step（2）The binder is silicone sealants, polyurethane adhesive, in epoxy adhesive at least
It is a kind of.
6. a kind of hollow ball shape carbonitride wraps up the preparation method of copper-based fuel-cell catalyst according to claim 1,
It is characterized in that：Step（2）Raw material in, in parts by weight, wherein：93 ~ 96 parts of colloid, 3 ~ 5 parts of pore creating material, 1 ~ 2 part of binder.
7. a kind of hollow ball shape carbonitride wraps up the preparation method of copper-based fuel-cell catalyst according to claim 1,
It is characterized in that：Step（2）The coating thickness is 300 ~ 500 μm.
8. a kind of hollow ball shape carbonitride wraps up the preparation method of copper-based fuel-cell catalyst according to claim 1,
It is characterized in that：Step（2）The temperature of the heat treatment is 800 ~ 1000 DEG C, and soaking time is 100 ~ 120min.
9. a kind of hollow ball shape carbonitride that any one of claim 1 ~ 8 the method is prepared wraps up copper-based fuel cell and urges
Agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110060884A (en) * | 2019-03-30 | 2019-07-26 | 南京理工大学 | A kind of preparation method of the high-performance flexible carbon film electrodes material based on biological fiber fabric |
| CN110354881A (en) * | 2019-06-25 | 2019-10-22 | 武汉大学 | A kind of NxThe preparation method of C coated metal nanoparticles Core-shell structure material |
| CN113428865A (en) * | 2021-08-30 | 2021-09-24 | 瑞浦能源有限公司 | Pomegranate-like silicon-based negative electrode material and preparation method thereof |
| CN115254171A (en) * | 2022-08-24 | 2022-11-01 | 江苏金聚合金材料有限公司 | High-dispersion copper-based ester hydrogenation catalyst with hollow core-shell structure and preparation method and application thereof |
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2018
- 2018-01-31 CN CN201810096482.3A patent/CN108281675A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110060884A (en) * | 2019-03-30 | 2019-07-26 | 南京理工大学 | A kind of preparation method of the high-performance flexible carbon film electrodes material based on biological fiber fabric |
| CN110354881A (en) * | 2019-06-25 | 2019-10-22 | 武汉大学 | A kind of NxThe preparation method of C coated metal nanoparticles Core-shell structure material |
| CN113428865A (en) * | 2021-08-30 | 2021-09-24 | 瑞浦能源有限公司 | Pomegranate-like silicon-based negative electrode material and preparation method thereof |
| CN113428865B (en) * | 2021-08-30 | 2021-10-29 | 瑞浦能源有限公司 | Pomegranate-like silicon-based negative electrode material and preparation method thereof |
| CN115254171A (en) * | 2022-08-24 | 2022-11-01 | 江苏金聚合金材料有限公司 | High-dispersion copper-based ester hydrogenation catalyst with hollow core-shell structure and preparation method and application thereof |
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Application publication date: 20180713 |