CN108411332A - A kind of preparation method generating ozone brown lead oxide compound film electrode - Google Patents
A kind of preparation method generating ozone brown lead oxide compound film electrode Download PDFInfo
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- CN108411332A CN108411332A CN201810152411.0A CN201810152411A CN108411332A CN 108411332 A CN108411332 A CN 108411332A CN 201810152411 A CN201810152411 A CN 201810152411A CN 108411332 A CN108411332 A CN 108411332A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/13—Ozone
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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Abstract
The present invention provides a kind of preparation methods generating ozone brown lead oxide compound film electrode, which is characterized in that includes the following steps：（1）Take SPE composite membranes spare；（2）Take modified graphene, PTFE emulsion, WC and brown lead oxide, appropriate absolute ethyl alcohol is added, 0.5 5h of freeze grinding at 20 DEG C 0 DEG C, after being fully ground dispersion, at 60 80 DEG C of water-bath then stirring is rolled into the brown lead oxide film of required thickness repeatedly to fibrosis bulk on the roller for being preheated to 30 70 DEG C；（3）By brown lead oxide film obtained, SPE films and conductive supporting net at 150 200 DEG C of hydraulic press, 5 10MPa 1 20min of hot pressing, take out, be cut into required size to get to the compound film electrode.The crystal grain of the electrode more refines and uniformly, current efficiency is improved, and efficiency of ozone generation is improved.
Description
Technical field
The present invention relates to a kind of preparation methods generating ozone brown lead oxide compound film electrode, are specifically a kind of modification
Graphene, polytetrafluoroethylene (PTFE)（PTFE）And tungsten carbide（WC）The lead dioxide electrode of doping.
Background technology
Preparing ozone by low-voltage electrolysis method is to be electrolysed oxygen-containing electrolyte using DC power supply.Wherein, low-voltage electrolysis water can obtain
Higher ozone concentration is obtained, and not will produce the harmful substances such as nitrogen oxides.Meanwhile the voltage of used DC power supply can be with
It is lied prostrate down to 3-5, it is safe and practical, convenient for promoting, for the method for preparing ozone first choice at present.
And electrolysis prepare ozone key problem be anode catalytic activity and stability, it is necessary to while having good
Electro catalytic activity and corrosion resistance.And electro catalytic activity and stability are not only related to electrode material, also with the structure of electrode and
Surface state etc. is because being known as much relations.Electrode structure and surface are still significantly improved space at present.
Invention content
Based on the above issues, the present invention provides the lead dioxide electrodes of a kind of modified graphene, PTFE and WC doping
Preparation method, compared with the prior art, the crystal grain of electrode more refines and uniformly, current efficiency is improved, and ozone generates effect
Rate is improved, meanwhile, the corrosion resistance of electrode also further improves, and improves the service life of electrode, reduces cost.
The solution of the present invention is as follows：A kind of generation ozone brown lead oxide compound film electrode, including：
SPE composite membranes；
The lead dioxide electrode that modified graphene, PTFE and the WC being deposited on composite membrane are adulterated.
The middle layer is prepared by thermal decomposition method；
The composite membrane is Nafion117 films.
Specifically, a kind of generation ozone preparation method of brown lead oxide compound film electrode, includes the following steps：
（1）Take SPE composite membranes spare；
（2）Modified graphene, PTFE emulsion, WC and brown lead oxide are taken, appropriate absolute ethyl alcohol is added, is freezed at -20 DEG C -0 DEG C
Grind 0.5-5h, after being fully ground dispersion, at 60-80 DEG C of water-bath stirring be then preheated to 30-70 DEG C to fibrosis bulk
Roller on be rolled into the brown lead oxide film of required thickness repeatedly；
（3）By brown lead oxide film obtained, SPE films and conductive supporting net at 150-200 DEG C of hydraulic press, 5-10MPa hot pressing 1-
20min takes out, and is cut into required size to get to the compound film electrode.
The mass ratio of the modified graphene and brown lead oxide is 1-10:1000, preferably 2-8:1000, more preferable 3-7:
1000。
The mass ratio of the PTFE and brown lead oxide is 5-20:1000, preferably 8-18:1000, more preferably 10-15:
1000。
The mass ratio of the WC and brown lead oxide is 3:15:1000, preferably 5-12:1000, more preferably 6-10:
1000。
The mass ratio of the absolute ethyl alcohol and brown lead oxide is 1-10:1, preferably 2-5:1.
The modified graphene is polyvinylpyrrolidone graft grapheme.The modified graphene preparation method is as follows：
（1）Graphene oxide is prepared using Hummers methods, graphite oxide is placed in one timing of homogenization in high pressure homogenizer
Between, 1-10 layers of graphene oxide is formed, is scattered in deionized water, dispersant and ultrasound is added, filemot oxidation is made
Graphene aqueous solution；
（2）Polyvinylpyrrolidone and reducing agent are sequentially added in graphene oxide water solution and are sufficiently stirred dissolving, oil bath
Heating reaction certain time, obtains the graphene of surface grafting polyvinylpyrrolidone under certain temperature.
The homogenization time is 1-5 hours.
The ultrasound is ultrasound 10-120 minutes at power 100-300W.
A concentration of 0.lmg/mL-2mg/mL of graphene aqueous solution.
The heating reaction temperature is 50-110 DEG C, reaction time 2-6h.
Catalyst can also be added in the heating reaction, and the catalyst includes Titanium series catalyst, tin catalyst etc..
The present invention is anti-by being esterified by simple method by polyvinylpyrrolidone hydrolysis in the presence of a reducing agent
Polyvinylpyrrolidone should be grafted on graphene.Graphene dispersion after modified is functional, and graphene is distributed more
Uniformly, and PbO can effectively be improved2Fineness of grain, so as to improve the catalytic efficiency of electrode.Moreover, graphite
Alkene specific surface area is up to 2630m2/ g can provide larger reaction interface for electrochemical reaction；Graphene electronic conductivity is about
105S/m contributes to the electric conductivity for improving composite material, therefore helps to improve the formation efficiency of ozone.
Polytetrafluoroethylene (PTFE) and WC chemical property are stablized, to improve the corrosion resistance of electrode, and the addition energy of PTFE
The reduction for the overpotential for oxygen evolution that the addition of enough improvement graphenes, WC is brought, is effectively improved the efficiency of ozone generation.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention is described in detail.
Preparation example：
The modified graphene is polyvinylpyrrolidone graft grapheme, and specific preparation method is as follows：
（1）Graphene oxide is prepared using Hummers methods, graphite oxide is placed in homogenization 2h in high pressure homogenizer, shape
It at 1-10 layers of graphene oxide, is scattered in deionized water, dispersant and ultrasound 60 minutes under 200W power is added, are made
Filemot graphene oxide water solution, concentration of aqueous solution 1mg/mL；
（2）Polyvinylpyrrolidone and reducing agent are sequentially added in graphene oxide water solution to and be sufficiently stirred dissolving, is added
Tetrabutyl titanate, heating reaction 2h, obtains the graphene of surface grafting polyvinylpyrrolidone at 82 DEG C of oil bath.
Embodiment 1：
The lead dioxide electrode preparation method of a kind of modified graphene, PTFE and WC doping includes the following steps：
（1）Take SPE composite membranes spare；
（2）Modified graphene, PTFE emulsion, WC and brown lead oxide are taken, appropriate absolute ethyl alcohol is added, the freeze grinding at -15 DEG C
1h, after being fully ground dispersion, at 70 DEG C of water-bath stirring then rolled repeatedly on the roller for being preheated to 40 DEG C to fibrosis bulk
It is pressed into the brown lead oxide film of required thickness；
（3）By brown lead oxide film obtained, SPE films and conductive supporting net at 180 DEG C of hydraulic press, 8MPa hot pressing 10min, take
Go out, is cut into required size to get to the compound film electrode.
The mass ratio of the modified graphene and brown lead oxide is 3:1000.
The mass ratio of the PTFE and brown lead oxide is 10:1000.
The mass ratio of the WC and brown lead oxide is 6:1000.
The mass ratio of the absolute ethyl alcohol and brown lead oxide is 2:1.
After tested, the electrode crystal grain obtained is tiny, uniform and fine and close, and size of microcrystal is 8-12 μm, and overpotential for oxygen evolution is
2180mV, current density 35mA/cm2Lower current efficiency is 21.4%.
Embodiment 2：
The lead dioxide electrode preparation method of a kind of modified graphene, PTFE and WC doping includes the following steps：
（1）Take SPE composite membranes spare；
（2）Modified graphene, PTFE emulsion, WC and brown lead oxide are taken, appropriate absolute ethyl alcohol is added, the freeze grinding at -15 DEG C
1h, after being fully ground dispersion, at 70 DEG C of water-bath stirring then rolled repeatedly on the roller for being preheated to 40 DEG C to fibrosis bulk
It is pressed into the brown lead oxide film of required thickness；
（3）By brown lead oxide film obtained, SPE films and conductive supporting net at 180 DEG C of hydraulic press, 8MPa hot pressing 10min, take
Go out, is cut into required size to get to the compound film electrode.
The mass ratio of the modified graphene and brown lead oxide is 5:1000.
The mass ratio of the PTFE and brown lead oxide is 12:1000.
The mass ratio of the WC and brown lead oxide is 8:1000.
The mass ratio of the absolute ethyl alcohol and brown lead oxide is 2:1.
After tested, the electrode crystal grain obtained is tiny, uniform and fine and close, and size of microcrystal is 8-12 μm, and overpotential for oxygen evolution is
2188mV, current density 35mA/cm2Lower current efficiency is 21.5%.
Embodiment 3：
The lead dioxide electrode preparation method of a kind of modified graphene, PTFE and WC doping includes the following steps：
（1）Take SPE composite membranes spare；
（2）Modified graphene, PTFE emulsion, WC and brown lead oxide are taken, appropriate absolute ethyl alcohol is added, the freeze grinding at -15 DEG C
1h, after being fully ground dispersion, at 70 DEG C of water-bath stirring then rolled repeatedly on the roller for being preheated to 40 DEG C to fibrosis bulk
It is pressed into the brown lead oxide film of required thickness；
（3）By brown lead oxide film obtained, SPE films and conductive supporting net at 180 DEG C of hydraulic press, 8MPa hot pressing 10min, take
Go out, is cut into required size to get to the compound film electrode.
The mass ratio of the modified graphene and brown lead oxide is 7:1000.
The mass ratio of the PTFE and brown lead oxide is 15:1000.
The mass ratio of the WC and brown lead oxide is 10:1000.
The mass ratio of the absolute ethyl alcohol and brown lead oxide is 2:1.
After tested, the electrode crystal grain obtained is tiny, uniform and fine and close, and size of microcrystal is 8-12 μm, and overpotential for oxygen evolution is
2191mV, current density 35mA/cm2Lower current efficiency is 20.3%.
Comparative example 1：
It is similar with embodiment 1 to prepare, only difference is that being added without modified graphene.After tested, the electrode grain particles obtained
Thicker and uneven, size of microcrystal is 16-20 μm, overpotential for oxygen evolution 2190mV, current density 35mA/cm2Lower current efficiency
It is 17.2%.
Comparative example 2：
Similar with embodiment 1 to prepare, only difference is that graphene and PVP is added, the two total content is equivalent for modified graphene.
After tested, the electrode crystal grain obtained is uniform, but grain size is thicker, and size of microcrystal is 13-18 μm, overpotential for oxygen evolution 2178mV, electricity
Current density 35mA/cm2Lower current efficiency is 18.5%.
It can be seen that from embodiment 1-3 by controlling modified graphene, PTFE and WC, oxygen analysed significantly reducing electrode
In the case of overpotential, the current efficiency of ozone preparation is significantly improved, and the optimal content of three, stone are found out by experiment
So that the catalytic performance of electrode is significantly improved, this can also from the comparison of embodiment 1 and comparative example 1 for the addition of black alkene
Find out.As can be seen that it is inadequate that PVP, which is only added, the presence of PVP is equal to electrode crystal grain distribution for comparative example 1 and comparative example 2
One property makes moderate progress, but the fineness of crystal grain is insufficient so that the current efficiency for generating ozone is relatively low.
Claims (10)
1. a kind of preparation method generating ozone brown lead oxide compound film electrode, which is characterized in that include the following steps：
（1）Take SPE composite membranes spare；
（2）Modified graphene, PTFE emulsion, WC and brown lead oxide are taken, appropriate absolute ethyl alcohol is added, is freezed at -20 DEG C -0 DEG C
Grind 0.5-5h, after being fully ground dispersion, at 60-80 DEG C of water-bath stirring be then preheated to 30-70 DEG C to fibrosis bulk
Roller on be rolled into the brown lead oxide film of required thickness repeatedly；
（3）By brown lead oxide film obtained, SPE films and conductive supporting net at 150-200 DEG C of hydraulic press, 5-10MPa hot pressing 1-
20min takes out, and is cut into required size to get to the compound film electrode.
2. according to the method described in claim 1, the mass ratio of the modified graphene and brown lead oxide is 1-10:1000, it is excellent
It is selected as 2-8:1000, more preferable 3-7:1000.
3. according to the method described in claim 1, the mass ratio of the PTFE and brown lead oxide is 5-20:1000, preferably 8-
18:1000, more preferably 10-15:1000.
4. according to the method described in claim 1, the mass ratio of the WC and brown lead oxide is 3:15:1000, preferably 5-12:
1000, more preferably 6-10:1000.
5. according to the method described in claim 1, the mass ratio of the absolute ethyl alcohol and brown lead oxide is 1-10:1, preferably 2-
5:1。
6. according to the method described in claim 1, the modified graphene is polyvinylpyrrolidone graft grapheme；It is described to change
Property graphene preparation method is as follows：
（1）Graphene oxide is prepared using Hummers methods, graphite oxide is placed in one timing of homogenization in high pressure homogenizer
Between, 1-10 layers of graphene oxide is formed, is scattered in deionized water, dispersant and ultrasound is added, filemot oxidation is made
Graphene aqueous solution；
（2）Polyvinylpyrrolidone and reducing agent are sequentially added in graphene oxide water solution and are sufficiently stirred dissolving, oil bath
Heating reaction certain time, obtains the graphene of surface grafting polyvinylpyrrolidone under certain temperature.
7. according to the method described in claim 6, the homogenization time is 1-5 hours.
8. according to the method described in claim 6, the ultrasound is ultrasound 10-120 minutes at power 100-300W.
9. according to the method described in claim 6, a concentration of 0.lmg/mL-2mg/mL of the graphene aqueous solution.
10. according to the method described in claim 6, the heating reaction temperature be 50-110 DEG C, reaction time 2-6h；It is preferred that
, catalyst is added in the heating reaction, and the catalyst includes Titanium series catalyst, tin catalyst.
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| CN201810152411.0A CN108411332B (en) | 2018-02-14 | 2018-02-14 | Preparation method of lead dioxide composite membrane electrode for generating ozone |
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Cited By (1)
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| CN109970155A (en) * | 2019-01-28 | 2019-07-05 | 中南大学 | A kind of preparation method of graphene oxide modification lead dioxide electrode |
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Cited By (2)
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