CN106868509B - A kind of graphene modified Lead dioxide anode modifiedby fluorine resin and preparation method thereof - Google Patents
A kind of graphene modified Lead dioxide anode modifiedby fluorine resin and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of graphene modified Lead dioxide anode modifiedby fluorine resin and preparation method thereof, tin-antimony oxide bottom, the α-PbO of the electrode2Middle layer and β-PbO2Contain graphene in active layer, preparation method includes the α-PbO of titanium plate pretreatment, the tin-antimony oxide bottom of heat deposition containing graphene, bioactive coating containing graphene2β-the PbO of middle layer, bioactive coating containing graphene2Active layer.The present invention has the advantages that the electrocatalytic oxidation activity and service life of graphene modified Lead dioxide anode modifiedby fluorine resin prepared by the present invention have raising by a relatively large margin than common Lead dioxide anode modifiedby fluorine resin, it is a kind of anode material suitable for Electro-catalytic Oxidation Process Organic Pollutants in Wastewater for having development potentiality.
Description
Technical field
The present invention relates to a kind of graphene modified lead dioxide electrodes and preparation method thereof, and are used for electrocatalytic oxidation
Degradation organic pollutants, belong to water treatment technology and electrochemical field.
Background technique
Electro-catalytic oxidation technology is with oxidability is strong, reaction rate is fast, equipment is simple, is easily manipulated, is without secondary pollution
The advantages that, it is a kind of suitable toxic, difficult for biological degradation organic wastewater water treatment technology of processing.Anode material is the core of the technology
The heart, wherein lead dioxide electrode is most promising one of electrocatalytic oxidation anode material, catalytic oxidation activity is high,
Good conductivity, corrosion resistance are strong, it is simple, cheap to prepare.But there are still current efficiency in use process for lead dioxide electrode
Low and service life needs the problems such as being further increased.Therefore, in recent years, a large amount of scholar be dedicated to lead dioxide electrode into
Row is effective modified, to improve the current efficiency and stability of lead dioxide electrode.Such as 102534652 A of patent CN is provided
A kind of titanium-based mixes the preparation method of tin lead dioxide electrode, and lead dioxide electrode surface obtained is uniform, fine and close, flawless,
With biggish specific surface area and higher electrocatalytic oxidation activity；101798690 A of patent CN provides one kind by main body lead salt
Lead acetate, acidity regulator sulfamic acid, solution additive sodium fluoride, solution additive ptfe emulsion component are constituted
The electroplate liquid of brown lead oxide, the smooth densification of prepared lead dioxide electrode, binding force is good, and catalytic activity is high, long service life；
103132076 A of patent CN provide a kind of lanthanum, gadolinium codope ti-supported lead dioxide electric pole preparation method, by lanthanum,
The synergistic effect of gadolinium codope, electrode have biggish specific surface area and more active site, are conducive to the migration of pollutant, inhale
Attached, desorption, can greatly improve the degradation effect to organic pollutant.Therefore, reasonable additive can effectively improve titanium dioxide
The catalysis oxidation ability and service life of lead electrode.
Graphene, SP2The hexatomic ring honeycomb-like network structural material that hydbridized carbon atoms are constituted not only has high chemical stabilization
Property, and there is brilliant electricity, optics, calorifics and mechanical property, the composite material as electrode can reduce resistance to mass tranfer,
Also unique conductive path can be provided for the fast transfer of charge and conduction.For this purpose, it is proposed that graphene is introduced into dioxy
In each film layer for changing lead electrode, to improve the electrocatalytic oxidation activity of electrode and the service life of electrode.
Summary of the invention
The object of the present invention is to provide a kind of graphene modified Lead dioxide anode modifiedby fluorine resins and preparation method thereof, and utilize
The electrode Electro-catalytic Oxidation Process organic pollutants, graphene modified Lead dioxide anode modifiedby fluorine resin obtained have electro-catalysis
The advantages that oxidation activity height, long service life, simple preparation method.
The object of the present invention is achieved like this, which includes:
Titanium base；
The tin-antimony oxide bottom of containing graphene of the heat deposition on Titanium base；
α-the PbO of containing graphene of the bioactive coating on tin-antimony oxide bottom2Middle layer；
Bioactive coating is in α-PbO2β-the PbO of containing graphene in middle layer2Active layer.
The preparation method of the graphene modified lead dioxide electrode the following steps are included:
1., the pretreatment of Titanium base: successively polish Titanium base until being in the sand paper of 120 mesh, 600 mesh and 1200 mesh first
Existing silvery white metallic luster；The Titanium base polished is sequentially placed into acetone and deionized water again and is ultrasonically treated 10 minutes, is gone
Except the greasy dirt and other impurity on titanium plate surface；Then by the Titanium base after ultrasonic treatment be immersed in oxalic acid etching liquid 80 DEG C ~
It is etched 2 hours under conditions of slightly boiled, taking-up is placed in oxalic acid preservation liquid and saves.
The oxalic acid etching liquid is that 150 grams of oxalic acid are dissolved in 1 liter of deionized water, heating stirring to dissolution prepare and
At；It is that 10 grams of oxalic acid are dissolved in 1 liter of deionized water that the oxalic acid, which saves liquid, and stirring to dissolution is formulated.
2., the preparation of the tin-antimony oxide bottom of containing graphene: the coating liquid containing graphene is coated on processing in 1.
On Titanium base surface afterwards, dried 10 minutes at 120 DEG C in electrically heated drying cabinet, then the Titanium base of drying is placed in Muffle furnace
It roasts 10 minutes at 300 DEG C, is so repeated 10 times, the calcining time in Muffle furnace is 1 hour for the last time, is naturally cooled to
Room temperature.
3., the α-PbO containing graphene2The preparation of middle layer: the 2. tin antimony oxygen with containing graphene that step is prepared
The Titanium base of compound bottom is as anode, and the stainless steel plate of homalographic is as cathode, in 100 milliliters of alkalinity platings containing graphene
Bioactive coating α-PbO in liquid2Middle layer, electrode spacing are 3cm, and the current density of electro-deposition is 3mA/cm2, depositing temperature is 40
DEG C, sedimentation time is 0.5 ~ 2 hour, there is ultrasonic wave added, supersonic frequency 40kHz, 100 ~ 600W of power in deposition process.Acoustic-electric
After deposition, it is washed with deionized water.
4., the β-PbO containing graphene2The preparation of active layer: by step 3. in the α-PbO containing graphene obtained2In
The Titanium base of interbed is as anode, and the stainless steel plate of homalographic is as cathode, in 100 milliliters of acidic baths for being mixed with graphene
Bioactive coating β-PbO2Active layer, electrode spacing are 3cm, and the current density of electro-deposition is 15mA/cm2, depositing temperature is 65 DEG C,
Sedimentation time is 0.5 ~ 2 hour, and plating solution volume is 100 milliliters, there is ultrasonic wave added in electrodeposition process, supersonic frequency 40kHz,
100 ~ 600W of power.After bioactive coating, it is washed with deionized water.
Step 2. described in coating liquid be that 20 grams of tin tetrachlorides and 2 grams of antimony trichlorides are added to 13 milliliters of mass concentrations
To stir to after being completely dissolved in 37% concentrated hydrochloric acid and 87 milliliters of isopropanol mixed liquors, 0.05 ~ 0.3 gram of graphene, stirring is added
Uniformly and ultrasound is formulated for 30 minutes.
Step 3. described in the alkali plating solution for being mixed with graphene be to be add to deionized water PbO and sodium hydroxide,
Heating stirring is completely dissolved to PbO, and after cooled to room temperature, graphene is added, stir evenly and ultrasound 30 minutes prepare and
At.The each component content of plating solution is 0.1 mol/L of PbO, 3.5 mol/L of sodium hydroxide, 0.5 ~ 5.0 grams per liter of graphene.
4. the acidic bath for being mixed with graphene is that plumbi nitras, sodium fluoride are added in nitric acid solution to step, is stirred
It mixes to after being completely dissolved, graphene is added, stir evenly and ultrasound 30 minutes made, each component content is graphene in plating solution
0.5 ~ 5.0 grams per liter, 0.5 mol/L of plumbi nitras, 1.0 mol/L of nitric acid, 0.05 mol/L of sodium fluoride.
Step 2., 3., 4. the graphene the preparation method comprises the following steps: clean graphite paper with dehydrated alcohol, deionized water, put
Enter in baking oven and is dried 1 hour at 60 DEG C.It is electrolysed under constant voltage using DC voltage-stabilizing constant-current switch power source, is made with graphite paper
For two electrode of yin-yang, the ammonium persulfate solution that 100 milliliters of mass concentrations are 0.4 % is electrolyte, and two electrode spacings are 2cm, electricity
Pressure is 20V.After powering on, a large amount of bubbles are had on anode graphite paper and are generated, while it is swollen to be observed that graphite paper occurs
Swollen and have floccule (graphene) to fall off, the color of electrolyte becomes light yellow.Floccule and deionized water mixture are carried out
Ultrasound is simultaneously cleaned with centrifugal process, is washed repeatedly 3 times, and to remove remaining ammonium persulfate, graphene is collected in drying later.
The present invention has a characteristic that
(1) tin-antimony oxide bottom, the α-PbO of the graphene modified Lead dioxide anode modifiedby fluorine resin prepared by the present invention2In
Interbed and β-PbO2Contain graphene in active layer, improve the electric conductivity of film layer, improves transfer of the charge in film layer
Speed.
(2) α-PbO of the present invention in preparation containing graphene2β-the PbO of middle layer and containing graphene2It is equal during active layer
Using bioactive coating technology, the degree of scatter of graphene in the plating solution is effectively increased, preparation process is simple, cheap.
(3) the graphene modified Lead dioxide anode modifiedby fluorine resin Electro-catalytic Oxidation Process phenol prepared by the present invention, in solution
Phenol removal rate improves 25.98% than common Lead dioxide anode modifiedby fluorine resin, and service life is up to common Lead dioxide anode modifiedby fluorine resin
2.6 again.
(4) difficult for biological degradation organic contamination in the graphene modified Lead dioxide anode modifiedby fluorine resin degradation water prepared by the present invention
Object, effect is obvious, convenient for management, and the processing method for being suitable for organic wastewater is independently operated, the preceding place that also can be used as bioanalysis
Reason technology and other technical tie-ups use.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of graphene modified Lead dioxide anode modifiedby fluorine resin of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of common Lead dioxide anode modifiedby fluorine resin.
Fig. 3 is the scanning electron microscope (SEM) photograph of graphene modified Lead dioxide anode modifiedby fluorine resin of the present invention.
Fig. 4 is the scanning electron microscope (SEM) photograph of surface layer graphene modified Lead dioxide anode modifiedby fluorine resin.
Fig. 5 is graphene modified Lead dioxide anode modifiedby fluorine resin of the present invention, the fluorine-containing titanium dioxide of surface layer graphene modified
The removal rate change curve of lead electrode and common Lead dioxide anode modifiedby fluorine resin Electro-catalytic Oxidation Process phenol.
Fig. 6 is graphene modified Lead dioxide anode modifiedby fluorine resin of the present invention, the fluorine-containing titanium dioxide of surface layer graphene modified
The accelerating lifetime testing curve graph of lead electrode and common Lead dioxide anode modifiedby fluorine resin in sulfuric acid solution.
Specific embodiment
For the ease of the comparison of product of the present invention, we are prepared for common Lead dioxide anode modifiedby fluorine resin, specific preparation method
It is as follows:
(1) Titanium base (30 millimeters × 50 millimeters × 0.8 millimeter) successively are polished with 120 mesh, 600 mesh and 1200 mesh sand paper,
Until silvery white metallic luster is presented in Titanium base, the Titanium base polished is sequentially placed into acetone and deionized water and is ultrasonically treated
10 minutes, remove the greasy dirt and other impurity of matrix surface；Then the Titanium base after ultrasonic treatment is immersed in oxalic acid etching liquid
In (oxalic acid etching liquid is that 150 grams of oxalic acid are dissolved in 1 liter of deionized water, and heating stirring to dissolution is formulated) 80 DEG C ~ it is micro-
It is etched 2 hours under the conditions of boiling, taking-up is placed on oxalic acid preservation liquid, and (it is that 10 grams of oxalic acid are dissolved in 1 liter of deionized water that oxalic acid, which saves liquid,
In, stirring is formulated to being completely dissolved) in save.
(2) tin tetrachloride and antimony trichloride are dissolved in concentrated hydrochloric acid and isopropyl alcohol mixture and coating liquid (coating liquid is made
It is that 20 grams of tin tetrachlorides and 2 grams of antimony trichlorides are added to 13 milliliters of mass concentrations to mix for 37% concentrated hydrochloric acid and 87 milliliters of isopropanols
Close in solution, stirring is formulated to being completely dissolved), it will be stored in the Titanium base that oxalic acid saves in liquid in step (1) and take out, benefit
With deionized water clean the surface, coating liquid is coated on clean Titanium base, dries 10 points at 120 DEG C in electrically heated drying cabinet
Clock, then the Titanium base after drying is placed in Muffle furnace at 300 DEG C and is roasted 10 minutes, it is so repeated 10 times, for the last time in horse
Not the calcining time in furnace is 1 hour, and cooled to room temperature obtains the Titanium base with tin-antimony oxide bottom.
(3) using the Titanium base with tin-antimony oxide bottom of step (2) preparation as anode, with the stainless steel of homalographic
Plate is as cathode, at 100 milliliters dissolved with electro-deposition α-in the alkali plating solution of 0.1 mol/L PbO and 3.5 mol/L sodium hydroxides
PbO2Middle layer, the current density of electro-deposition are 3mA/cm2, depositing temperature is 40 DEG C, and sedimentation time is 1 hour.Use deionized water
After cleaning, obtain with α-PbO2The Titanium base of middle layer.
(4) step (3) preparation is had into α-PbO2The Titanium base of middle layer is made as anode, the stainless steel plate of homalographic
For cathode, plated in 100 milliliters of acidity containing 0.5 mol/L plumbi nitras, 0.05 mol/L sodium fluoride and 1 mol/L nitric acid
Electro-deposition β-PbO in liquid2Surface-active layer, electro-deposition current density are 15mA/cm2, depositing temperature is 65 DEG C, and sedimentation time is 1
Hour, the common Lead dioxide anode modifiedby fluorine resin prepared, as shown in Fig. 2: as can be seen from Fig., common fluorine-containing titanium dioxide
Lead electrode is accumulated by a large amount of pyramid brown lead oxide crystal grains.
Use the common Lead dioxide anode modifiedby fluorine resin being prepared for anode, the stainless steel plate of homalographic is cathode, electrode
Spacing is 1 centimetre, Electrocatalytic Oxidation of Phenol in Water, and the concentration of phenol is 50 mg/litres, and the sodium sulphate of 0.05 mol/L props up
Electrolyte is held, the volume of solution is 200 milliliters, and electrocatalytic oxidation current density is 30mA/cm2, temperature is 30 DEG C, degradation process
Phenol removal rate curve such as attached drawing 5, the removal rate of phenol is 72.26% after reaction 120 minutes.
Using the common Lead dioxide anode modifiedby fluorine resin being prepared as anode, platinum electrode is cathode, in the sulfuric acid of 1 mol/L
In solution, 1A/cm2Current density under, measure accelerated aging curve such as attached drawing 6, the reinforcing of common Lead dioxide anode modifiedby fluorine resin
Service life is about 51 hours.
The specific embodiment for preparing product of the present invention is as follows:
Embodiment 1:
As shown in Fig. 1: the structure of graphene modified Lead dioxide anode modifiedby fluorine resin of the invention includes:
Titanium base 1；
The tin-antimony oxide bottom 2 of containing graphene of the heat deposition on Titanium base；
α-the PbO of containing graphene of the bioactive coating on bottom 22Middle layer 3；
β-the PbO of containing graphene of the bioactive coating in middle layer 32Active layer 4.
The preparation method is as follows:
(1) graphite paper is cleaned with dehydrated alcohol, deionized water, is put into baking oven at 60 DEG C and dries 1 hour.It is steady using direct current
Pressure constant-current switch power source is electrolysed under constant voltage, and using graphite paper as two electrode of yin-yang, 100 milliliters of mass concentrations are 0.4%
Ammonium persulfate solution be electrolyte, two electrode spacings be 2cm, voltage be 20 V.After powering on, the meeting on anode graphite paper
There are a large amount of bubbles to generate, while being observed that graphite paper expands and has floccule (graphene) to fall off, the face of electrolyte
Discoloration is light yellow.Floccule and deionized water mixture are subjected to ultrasound and cleaned with centrifugal process, is washed repeatedly 3 times,
To remove remaining ammonium persulfate, graphene is collected in drying later.
(2) Titanium base (30 millimeters × 50 millimeters × 0.8 millimeter) successively are polished with 120 mesh, 600 mesh and 1200 mesh sand paper,
Until silvery white metallic luster is presented in Titanium base, the Titanium base polished is sequentially placed into acetone and deionized water and is ultrasonically treated
10 minutes, remove the greasy dirt and other impurity of matrix surface；Then the Titanium base after ultrasonic treatment is immersed in oxalic acid etching liquid
In (oxalic acid etching liquid is that 150 grams of oxalic acid are dissolved in 1 liter of deionized water, and heating stirring is formulated to being completely dissolved) at 80 DEG C
~ it is slightly boiled under the conditions of etch 2 hours, taking-up be placed on oxalic acid save liquid (oxalic acid save liquid be that 10 grams of oxalic acid are dissolved in 1 liter of deionization
In water, stirring is formulated to being completely dissolved) in save.
(3) 20 grams of tin tetrachlorides and 2 grams of antimony trichlorides are dissolved in 13 milliliters of mass concentrations is that 37% concentrated hydrochloric acid and 87 milliliters are different
In propyl alcohol mixed solution, 0.1 gram of graphene is added, stirs evenly and 30 minutes ultrasonic, coating liquid is made, will be protected in step (2)
There are oxalic acid to save the Titanium base taking-up in liquid, and using deionized water clean the surface, coating liquid is evenly applied to clean titanium
On matrix, dried 10 minutes at 120 DEG C in electrically heated drying cabinet, then the Titanium base after drying is placed in Muffle furnace at 300 DEG C
Roasting 10 minutes, is so repeated 10 times, and the calcining time in Muffle furnace is 1 hour for the last time, and cooled to room temperature obtains
To the Titanium base of the tin-antimony oxide bottom with containing graphene.
(4) 0.1 gram of graphene is added to 100 milliliters dissolved with 0.1 mol/L PbO and 3.5 mol/L sodium hydroxides
In solution, stirs evenly and 30 minutes ultrasonic, the alkali plating solution for being mixed with graphene is made.By step (3) preparation with containing stone
The Titanium base of the tin-antimony oxide bottom of black alkene is as anode, using the stainless steel plate of homalographic as cathode, in above-mentioned alkalinity plating
Bioactive coating α-PbO in liquid2Middle layer, electrode spacing are 3cm, and the current density of electro-deposition is 3mA/cm2, depositing temperature is 40
DEG C, sedimentation time is 1 hour, there is ultrasonic wave added, supersonic frequency 40kHz, power 200W in electrodeposition process.Bioactive coating knot
It is washed with deionized water after beam, obtains the α-PbO with containing graphene2The Titanium base of middle layer.
(5) 0.1 gram of graphene is added to 100 milliliters dissolved with 0.5 mol/L plumbi nitras, 0.05 mol/L sodium fluoride
In 1 mol/L nitric acid solution, stirs evenly and 30 minutes ultrasonic, the acidic bath for being mixed with graphene is made.Step (4) are made
Standby α-the PbO with containing graphene2The Titanium base of middle layer is as anode, and the stainless steel plate of homalographic is as cathode, upper
State bioactive coating β-PbO in acidic bath2Surface-active layer, electro-deposition current density are 15mA/cm2, depositing temperature is 65 DEG C,
Sedimentation time is 1 hour, there is ultrasonic wave added, supersonic frequency 40kHz, power 200W in electrodeposition process, and bioactive coating terminates
After be washed with deionized water, obtain graphene modified Lead dioxide anode modifiedby fluorine resin, as shown in Fig. 3: from the figure 3, it may be seen that preparation
The surfacing of graphene modified Lead dioxide anode modifiedby fluorine resin, densification, β-PbO2Crystal grain size is significantly less than common fluorine-containing two
Lead dioxide electrode.
Use the graphene modified Lead dioxide anode modifiedby fluorine resin being prepared for anode, the stainless steel plate of homalographic is yin
The concentration of pole, Electrocatalytic Oxidation of Phenol in Water, phenol is 50 mg/litres, and the sodium sulphate of 0.05 mol/L does supporting electrolyte,
The volume of solution is 200 milliliters, and electrode spacing is 1 centimetre, and electrocatalytic oxidation current density is 30mA/cm2, temperature is 30 DEG C,
Degradation process phenol removal rate curve such as attached drawing 5, the removal rate of phenol is 91.03% after reaction 120 minutes, than common by fluorine-containing two
Lead dioxide electrode improves 25.98%.
Using the graphene modified Lead dioxide anode modifiedby fluorine resin being prepared as anode, platinum electrode is cathode, in 1 mol/L
Sulfuric acid solution in, 1A/cm2Current density under, measure accelerated aging curve such as attached drawing 6, the fluorine-containing titanium dioxide of graphene modified
Lead electrode reinforcing life is about 134 hours, is 2.6 times of common Lead dioxide anode modifiedby fluorine resin.
Embodiment 2:
The preparation method is the same as that of Example 1 for electrode.
Except that α-the PbO of bioactive coating containing graphene2β-the PbO of middle layer and containing graphene2The plating solution of active layer
The concentration of middle graphene is 0.5 grams per liter, obtains graphene modified Lead dioxide anode modifiedby fluorine resin.
Use the graphene modified Lead dioxide anode modifiedby fluorine resin being prepared for anode, the stainless steel plate of homalographic is yin
Pole, electrode spacing are 1 centimetre, and Electrocatalytic Oxidation of Phenol in Water, the concentration of phenol is 50 mg/litres, the sulfuric acid of 0.05 mol/L
Sodium does supporting electrolyte, and the volume of solution is 200 milliliters, and electrode spacing is 1 centimetre, and electrocatalytic oxidation current density is 30mA/
cm2, temperature is 30 DEG C, and the removal rate of phenol is 86.55% after reaction 120 minutes.
Using the graphene modified Lead dioxide anode modifiedby fluorine resin being prepared as anode, platinum electrode is cathode, in 1 mol/L
Sulfuric acid solution in, 1A/cm2Current density under, the reinforcing life for measuring electrode is about 95 hours, for common fluorine-containing titanium dioxide
1.86 times of lead electrode.
Currently, common lead dioxide electrode method of modifying is that active material is entrained in β-PbO2In surface-active layer,
Therefore we are prepared for only in β-PbO2Lead dioxide anode modifiedby fluorine resin (the referred to hereinafter as surface layer stone of doped graphene in surface-active layer
Black alkene modifies Lead dioxide anode modifiedby fluorine resin), for being carried out with graphene modified lead dioxide electrode made from the embodiment of the present invention 1
Comparative studies.
The preparation step of surface layer graphene modified Lead dioxide anode modifiedby fluorine resin contains with graphene modified in the embodiment of the present invention 1
Fluorodioxy lead electrode is identical, the difference is that in tin-antimony oxide middle layer and α-PbO2Without graphene in middle layer preparation process
It is added, α-PbO2Also without ultrasonic wave added in middle layer preparation process.Gained surface layer graphene modified Lead dioxide anode modifiedby fluorine resin, such as
Shown in attached drawing 4: it is found that the flatness on the surface layer graphene modified Lead dioxide anode modifiedby fluorine resin surface of preparation compared with attached drawing 3
It is poor compared with graphene modified lead dioxide electrode in the embodiment of the present invention 1 with compactness, and crystal grain is uneven.
Use the surface layer graphene modified Lead dioxide anode modifiedby fluorine resin being prepared for anode, the stainless steel plate of homalographic is
Cathode, electrode spacing are 1 centimetre, and Electrocatalytic Oxidation of Phenol in Water, the concentration of phenol is 50 mg/litres, the sulphur of 0.05 mol/L
Sour sodium does supporting electrolyte, and the volume of solution is 200 milliliters, and electrode spacing is 1 centimetre, and electrocatalytic oxidation current density is
30mA/cm2, temperature is 30 DEG C, and degradation process phenol removal rate curve such as attached drawing 5, the removal rate of phenol is after reaction 120 minutes
82.11%, hence it is evident that lower than the removal rate of graphene modified Lead dioxide anode modifiedby fluorine resin Pyrogentisinic Acid in the embodiment of the present invention 1
(91.03%).
Using the surface layer graphene modified Lead dioxide anode modifiedby fluorine resin being prepared as anode, platinum electrode is cathode, is rubbed in 1
You/liter sulfuric acid solution in, 1A/cm2Current density under, measure accelerated aging curve such as attached drawing 6, surface layer graphene modified contains
Fluorodioxy lead electrode reinforcing life is about 78 hours, is 1.53 times of common Lead dioxide anode modifiedby fluorine resin, and the present invention is implemented
Graphene modified Lead dioxide anode modifiedby fluorine resin reinforcing life is about 134 hours in example 1, is common Lead dioxide anode modifiedby fluorine resin
2.6 again.
Claims (5)
1. a kind of graphene modified Lead dioxide anode modifiedby fluorine resin, which includes Titanium base, tin-antimony oxide bottom, α-PbO2In
Interbed and β-PbO2Active layer, it is characterised in that: tin-antimony oxide bottom, the α-PbO of the electrode2Middle layer and β-PbO2Activity
Contain graphene in layer；Wherein, the tin-antimony oxide bottom of containing graphene is using heat sink area method, by the painting containing graphene
Covering liquid is evenly applied on pretreated Titanium base surface, is dried 10 minutes at 120 DEG C in electrically heated drying cabinet, then will drying
Titanium base be placed in Muffle furnace at 300 DEG C and roast 10 minutes, be so repeated 10 times, when roasting in Muffle furnace for the last time
Between be 1 hour, cooled to room temperature；
α-the PbO of containing graphene2Middle layer is using bioactive coating method, and using the electrode of above-mentioned preparation as anode, homalographic is not
Rust steel plate is as cathode, the bioactive coating α-PbO in 100 milliliters of alkali plating solutions for being mixed with graphene2Middle layer, electrode spacing are
3cm, the current density of electro-deposition are 3mA/cm2, depositing temperature is 40 DEG C, and sedimentation time is 0.5-2 hours, is had in deposition process
Ultrasonic wave added, supersonic frequency 40kHz, power are 100~600W；After bioactive coating, it is washed with deionized water；
β-the PbO of containing graphene2Active layer is using bioactive coating method, and using the electrode of above-mentioned preparation as anode, homalographic is not
Rust steel plate is as cathode, the bioactive coating β-PbO in 100 milliliters of acidic baths for being mixed with graphene2Active layer, electrode spacing are
3cm, the current density of electro-deposition are 15mA/cm2, depositing temperature is 65 DEG C, and sedimentation time is 0.5-2 hours, and plating solution volume is
100 milliliters, there are ultrasonic wave added, supersonic frequency 40kHz in electrodeposition process, power is 100~600W；Bioactive coating terminates
Afterwards, it is washed with deionized water.
2. a kind of preparation method of graphene modified Lead dioxide anode modifiedby fluorine resin, it is characterised in that: the following steps are included:
(1) pretreatment of Titanium base；
(2) it is pre- that the coating liquid containing graphene the tin-antimony oxide bottom of heat deposition containing graphene: is evenly applied to step (1)
On treated Titanium base surface, dried 10 minutes at 120 DEG C in electrically heated drying cabinet, then the Titanium base of drying is placed in Muffle
It roasts 10 minutes at 300 DEG C in furnace, is so repeated 10 times, the calcining time in Muffle furnace is 1 hour for the last time, naturally cold
But to room temperature；
(3) α-PbO of bioactive coating containing graphene2Middle layer: using the electrode of step (2) preparation as anode, homalographic it is stainless
Steel plate is as cathode, the bioactive coating α-PbO in 100 milliliters of alkali plating solutions for being mixed with graphene2Middle layer, electrode spacing are
3cm, the current density of electro-deposition are 3mA/cm2, depositing temperature is 40 DEG C, and sedimentation time is 0.5-2 hours, is had in deposition process
Ultrasonic wave added, supersonic frequency 40kHz, power are 100~600W；After bioactive coating, it is washed with deionized water；
(4) β-PbO of bioactive coating containing graphene2Active layer: using the electrode of step (3) preparation as anode, homalographic it is stainless
Steel plate is as cathode, the bioactive coating β-PbO in 100 milliliters of acidic baths for being mixed with graphene2Active layer, electrode spacing are
3cm, the current density of electro-deposition are 15mA/cm2, depositing temperature is 65 DEG C, and sedimentation time is 0.5-2 hours, and plating solution volume is
100 milliliters, there are ultrasonic wave added, supersonic frequency 40kHz in electrodeposition process, power is 100~600W；Bioactive coating terminates
Afterwards, it is washed with deionized water.
3. a kind of preparation method of graphene modified Lead dioxide anode modifiedby fluorine resin according to claim 2, it is characterised in that:
Coating liquid containing graphene described in step (2) is that 20 grams of tin tetrachlorides and 2 grams of antimony trichlorides are added to 13 milliliters of matter
Measuring concentration is to stir in 37% concentrated hydrochloric acid and 87 milliliters of isopropanol mixed liquors to after being completely dissolved, and 0.05~0.3 gram of graphite is added
Alkene, stir evenly and ultrasound be formulated within 30 minutes.
4. a kind of preparation method of graphene modified Lead dioxide anode modifiedby fluorine resin according to claim 2, it is characterised in that:
The alkali plating solution that graphene is mixed with described in step (3) is to be add to deionized water PbO and sodium hydroxide, and heating stirring is extremely
PbO is completely dissolved, and after cooled to room temperature, graphene is added, and stirs evenly and ultrasound is formulated for 30 minutes；Plating solution it is each
Constituent content is 0.1 mol/L of PbO, 3.5 mol/L of sodium hydroxide, 0.5~5.0 grams per liter of graphene.
5. a kind of preparation method of graphene modified Lead dioxide anode modifiedby fluorine resin according to claim 2, it is characterised in that:
The acidic bath that graphene is mixed with described in step (4) is that plumbi nitras, sodium fluoride are added in nitric acid solution, is stirred to complete
After dissolution, graphene is added, stirs evenly and ultrasound 30 minutes made, each component content is graphene 0.5~5.0 in plating solution
Grams per liter, 0.5 mol/L of plumbi nitras, 1.0 mol/L of nitric acid, 0.05 mol/L of sodium fluoride.
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