CN105336962B - A kind of three-phase composite electrode of vanadium cell and preparation method thereof - Google Patents
A kind of three-phase composite electrode of vanadium cell and preparation method thereof Download PDFInfo
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- CN105336962B CN105336962B CN201510681963.7A CN201510681963A CN105336962B CN 105336962 B CN105336962 B CN 105336962B CN 201510681963 A CN201510681963 A CN 201510681963A CN 105336962 B CN105336962 B CN 105336962B
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- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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Abstract
The invention discloses a kind of three-phase composite electrode, belong to electrode field.A kind of three-phase composite electrode of the present invention is by sulfonated graphene, manganese dioxide and manganese dioxide/poly-（3,4 ethene dioxythiophenes）Polystyrolsulfon acid is constituted.The present invention a kind of three-phase composite electrode have weaken graphite electrode etching phenomenon, improve vanadium cell service life, increase vanadium cell use it is safe the characteristics of.
Description
Technical field
The present invention relates to a kind of electrode, particularly a kind of three-phase composite electrode.
Background technology
Vanadium oxide reduction flow battery is a kind of model electrochemical energy storage device, by battery pile, positive and negative electrolyte reservoir and
Other sub-controlling unit compositions.Vanadium cell is in addition to the characteristics of possessing general redox flow batteries, and vanadium cell is with difference
The vanadium ion solution of valence state is battery plus-negative plate active material, is eliminated due to the battery failure that electrolyte cross pollution is caused；
Vanadium cell will not substantially be produced to human body and the harmful material of environment in the production and use process；While the price of vanadium cell
Cheaply, energy efficiency is high, and service life is long, and reliability is high, and operation and maintenance expense is low, is a kind of outstanding energy-storage system.I
State is the abundant country of vanadium resource.Verified in the world in vanadium reserves, Chinese occupancy volume occupies third place in the world；And current China
V2O5Annual production occupies the 4th, the world up to 21,010,000 tons.Development and utilization vanadium cell has special resources advantage in China.
The electrode of prior art vanadium cell uses graphite material, but positive pole side graphite cake has etching phenomenon, Yi Zao
Into battery leakage accident, the use of vanadium cell is caused to there is serious potential safety hazard.
The content of the invention
The goal of the invention of the present invention is：Show for above-mentioned problem there is provided a kind of etching for weakening graphite electrode
As improving vanadium cell service life, the safe three-phase composite electrode that increase vanadium cell is used.
The technical solution adopted by the present invention is as follows：
A kind of three-phase composite electrode of the present invention, by sulfonated graphene, manganese dioxide and manganese dioxide/poly-（3,4- ethene
Dioxy thiophene）- polystyrolsulfon acid is constituted.
Due to using above-mentioned technical proposal, the special construction of graphene make it have high-specific surface area, high mechanical properties and
High conductivity, but irreversible reunion easily occurs for graphene, greatly reduces available active surface, and its specific capacitance is relatively low.
Sulfonic functional graphene can improve electrode in the electrodes with the high charged group of high electric conductivity and surface
Electric conductivity, obstructs the absorption of counter ion, so as to improve current efficiency and desalination amount again.Manganese dioxide has specific volume high, valency
Lattice are low, the characteristics of environmentally friendly, but the electric conductivity of manganese dioxide, and mechanical stability is relatively poor, gather（3,4- ethylene dioxy thiophenes
Fen）The conjugated structure of-polystyrolsulfon acid causes it to have good electric conductivity, with good invertibity and excellent leads
Electrically.This three is combined, using the synergy between each component, its cyclical stability and charge and discharge can be effectively improved
Electric invertibity, improve the combination property of electrode, it is to avoid graphite cake has etching phenomenon in the prior art, so as to reduce battery
The generation of leakage accident, greatly eliminates the potential safety hazard during the use of vanadium cell.
A kind of three-phase composite electrode of the present invention, the manganese dioxide is plated on sulfonated graphene surface, described poly-（3,4-
Ethene dioxythiophene）- polystyrolsulfon acid is plated on manganese dioxide layer surface.
A kind of three-phase composite electrode of the present invention, it is characterised in that made using following steps：
Step one：Weigh a certain amount of potassium peroxydisulfate and phosphorus pentoxide is dissolved in the concentrated sulfuric acid, graphite is added, at 80 DEG C
Under the conditions of, 4 ~ 5h is reacted, is cooled to after room temperature, is filtered, is dried, is obtained solid A, solid A is well mixed with the concentrated sulfuric acid, 0 ~
It is 1 in molar ratio under conditions of 5 DEG C:1 adds after potassium permanganate, 2 ~ 3h of reaction, adds appropriate hydrogen peroxide, obtains yellow and sink
Form sediment, dried after yellow mercury oxide is filtered；
Step 2：Weigh a certain amount of p-aminobenzene sulfonic acid and be dissolved in the sodium hydroxide solution that appropriate mass fraction is 2%,
P-aminobenzene sulfonic acid is pressed under conditions of 0 DEG C：The mass ratio of natrium nitrosum is 2:1 condition adds natrium nitrosum, by amino
Benzene sulfonic acid：The mol ratio 20 of hydrochloric acid:1 is added drop-wise to hydrochloric acid in solution, and white precipitate is made, and is dried after filtering；
Step 3：By obtained yellow mercury oxide and NaBH in step one4In molar ratio 1:1.5 uniform mixing are fallen back
In, by obtained white precipitate in mass ratio 1 in step 2：1.2 are added to the water, and 5 ~ 6h is reacted under conditions of not higher than 0 DEG C,
Yellow mercury oxide is pressed into system again：The mol ratio 1 of hydrazine hydrate：1 adds hydrazine hydrate, and sulfonated graphene dispersion liquid is made；
Step 4：By obtained sulfonated graphene homogeneous dispersion drop coating is on ito glass in step 3, in 0.1mol/L
MnSO4In the electrolyte of solution, using sulfonated graphene electrode as working electrode, Ag/AgCl is reference electrode, and platinum filament is to electricity
Pole, 5 ~ 6min is reacted in 1.0V voltages, sulfonated graphene/manganese dioxide composite electrode is obtained at room temperature；
Step 5：0.05mol/L 3,4- ethene dioxythiophenes-styrene sulfonic acid is dissolved in 0.1mol/L Na2SO4Solution
In, as supporting electrolyte, using sulfonated graphene/manganese dioxide as working electrode, Ag/AgCl is reference electrode, platinum filament for pair
Electrode, reacts 5 ~ 6min in 1.0V voltages at room temperature, obtains sulfonated graphene/manganese dioxide/poly-（3,4- ethylene dioxy thiophenes
Fen）- polystyrolsulfon acid three-phase composite electrode.
A kind of vanadium cell of the three-phase composite electrode of the application present invention, including electrolyte, and the ion being placed in electrolyte
Film, the ionic membrane both sides are respectively equipped with electrode, the electrode base insertion electrolyte；The ionic membrane is multilayer material,
The electrolyte is the V (III) comprising additive/V (IV) sulfuric acid solution system mixed electrolytic solution, and the electrode is sulfonation stone
Black alkene/manganese dioxide/poly-（3,4- ethene dioxythiophenes）- polystyrolsulfon acid three-phase composite electrode.
By adopting the above-described technical solution, being improved the ionic membrane of prior art, not only ensure ion of knowing clearly
Proton conductivity, chemical stability, thermal stability and the mechanical performance of film, while reducing vanadium ion permeability, significantly
Improve the energy efficiency of battery；Using graphene combination electrode, there is etching in the electrode for solving vanadium cell in the prior art
Phenomenon；Improvement to electrolyte improves the invertibity of electrode reaction, improves the stability of electrolyte, reduces vanadium ion knot
Brilliant appearance, improves energy content of battery efficiency.
A kind of vanadium cell of application three-phase composite electrode, the ionic membrane includes cell nafion proton membrane one, the perfluor
The lower floor of sulfonic acid proton membrane one is covered with silicon dioxide layer, and the lower floor of the silica is covered with cell nafion proton membrane two；
The thickness of the silicon dioxide layer is 300-400nm；The surface of cell nafion proton membrane one is covered with phthalic acid diethyl two
Alcohol diacrylate ester layer, the surface of cell nafion proton membrane two is covered with PSS layer；Include matter in the electrolyte
Measure the formic acid that fraction is 1.2 ~ 1.8%, 0.12 ~ 0.15% p-methyl benzenesulfonic acid and 2.5 ~ 3.1% 3- [3- (courage amido propyl) two
Methylamino] propane sulfonic acid inner salt.
By adopting the above-described technical solution, PDDA layer and PSS layer energy
The crosslinking to sulfonic acid group in cell nafion proton membrane is enough realized, the aqueous of film is improved while vanadium ion permeability is reduced
Amount so that proton is easier to pass freely through, and further increases the proton conductivity and energy efficiency of ionic membrane, p-methyl benzenesulfonic acid
The invertibity of electrode process can be improved, electrochemistry polarity is reduced, it is helpful to improving energy content of battery efficiency；Negative pole can be reduced
The viscosity of liquid, reduces the kinetic energy loss of pump and the resistance to mass tranfer of reduction electrode process, but p-methyl benzenesulfonic acid can also reduce negative pole
The electrical conductivity of liquid, increases the internal resistance of cell；Formic acid improves the stability of mixed electrolytic solution, has very to trivalent and tetravalent vanadium ion
Good stabilization, improves the chemical property of electrolyte and the reactivity of electrolyte, so as to weaken p-methyl benzenesulfonic acid
Influence to electrical conductivity；3- [3- (courage amido propyl) dimethylamino] propane sulfonic acid inner salt is zwitterionic surfactant, is improved
The solubility of vanadium ion, reduces to crystallize in electrolyte and occurs, and improves the invertibity of electrode reaction, while also changing well
It has been apt to V4+Heat endurance.
In summary, by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1st, electrode cycle stability and discharge and recharge invertibity are effectively improved, the combination property of electrode is improved, it is to avoid
In the prior art there is etching phenomenon in graphite cake, so as to reduce the generation of battery leakage accident, greatly eliminate making for vanadium cell
Potential safety hazard during.
2nd, vanadium permeability is substantially reduced, but not influences passing through for proton, it is ensured that the proton conductivity of ionic membrane,
The energy efficiency of battery is improved, the invertibity of electrode reaction is improved, the stability of electrolyte is improved, reduces vanadium ion
The appearance of crystallization, adds V4+The heat endurance of ion.
Embodiment
The present invention is described in detail below.
In order that the object, technical solution and advantage of invention are more clearly understood, with reference to embodiments, the present invention is entered
Row is further described.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, limit is not used to
The fixed present invention.
The phosphorus pentoxide of the potassium peroxydisulfate and 1.5g that weigh 1g is dissolved in the concentrated sulfuric acid, 5g graphite is added, in 80 DEG C of bar
Under part, 4h is reacted, is cooled to after room temperature, filtered, dried, obtain solid A, solid A is mixed with 10mL 90% concentrated sulfuric acid
It is even, added under conditions of 0 DEG C after 29.25g potassium permanganate, reaction 2h, add 2mL hydrogen peroxide, obtain yellow mercury oxide,
Dried after yellow mercury oxide is filtered.The p-aminobenzene sulfonic acid for weighing 2g is dissolved in the sodium hydroxide solution that 15mL mass fractions are 2%,
P-aminobenzene sulfonic acid is pressed under conditions of 0 DEG C：The mass ratio of natrium nitrosum is 2:1 condition adds natrium nitrosum, by amino
Benzene sulfonic acid：The mol ratio 20 of hydrochloric acid:1 is added drop-wise to hydrochloric acid in solution, and white precipitate is made, and is dried after filtering.By obtained Huang
Color is precipitated and NaBH4In molar ratio 1:During 1.5 uniform mixing are fallen back, obtained white precipitate is pressed into white precipitate：Yellow
The mass ratio 1 of precipitation：1.2 are added to the water, and 5h is reacted under conditions of not higher than 0 DEG C, then into system by yellow mercury oxide：Hydration
The mol ratio 1 of hydrazine：1 adds hydrazine hydrate, and sulfonated graphene dispersion liquid is made.By obtained sulfonated graphene homogeneous dispersion drop coating
On ito glass, in 0.1mol/L MnSO4In the electrolyte of solution, using sulfonated graphene electrode as working electrode, Ag/AgCl
For reference electrode, platinum filament is, to electrode, to react 5min in 1.0V voltages at room temperature, obtain sulfonated graphene/manganese dioxide multiple
Composite electrode.0.05mol/L 3,4- ethene dioxythiophenes-styrene sulfonic acid is dissolved in 0.1mol/L Na2SO4In solution, as
Supporting electrolyte, using sulfonated graphene/manganese dioxide as working electrode, Ag/AgCl is reference electrode, and platinum filament is to electrode, room
5min is reacted in 1.0V voltages under temperature, sulfonated graphene/manganese dioxide/poly- is obtained（3,4- ethene dioxythiophenes）- polyphenyl second
Alkene sulfonic acid three-phase composite electrode.
A kind of vanadium cell of application three-phase composite electrode, including electrolyte, and the ionic membrane being placed in electrolyte, ionic membrane
Both sides are respectively equipped with electrode, electrode base insertion electrolyte.
Ionic membrane is multilayer material, and electroplating a layer thickness in the lower floor of cell nafion proton membrane one by pretreatment is
300nm silicon dioxide layer, then electroplate one layer of cell nafion proton membrane two in silicon dioxide layer lower floor.In cell nafion proton membrane
One layer of PDDA layer is electroplated in one upper surface, in the lower surface electricity of cell nafion proton membrane two
One layer of PSS layer of plating, that is, be made the ionic membrane with sandwich construction.
By analytically pure V2O3And V2O5According to 1：1 mass ratio uniformly after mixing, weighs 10g, adds to the 90% of 20mL
In concentrated sulfuric acid solution, be heated to reflux under conditions of 120 DEG C, naturally cool to after room temperature filter, obtain containing three, tetravalence vanadium from
The mixed electrolytic solution of son；Weigh 0.56g formic acid, 0.056g p-methyl benzenesulfonic acid, 1.16g 3- [3- (courage amido propyl) two
Methylamino] propane sulfonic acid inner salt is dissolved in redistilled water, be poured slowly into the state of at the uniform velocity stirring containing three, tetravalence vanadium from
The mixed electrolytic solution of son, is obtained containing the formic acid that mass fraction is 1.2%, 0.12% p-methyl benzenesulfonic acid and 2.5% 3- [3- (courages
Amido propyl) dimethylamino] propane sulfonic acid inner salt mixed electrolytic solution.
Embodiment 2
The phosphorus pentoxide of the potassium peroxydisulfate and 1.5g that weigh 1g is dissolved in the concentrated sulfuric acid, 5g graphite is added, in 80 DEG C of bar
Under part, 5h is reacted, is cooled to after room temperature, filtered, dried, obtain solid A, solid A is mixed with 10mL 90% concentrated sulfuric acid
It is even, added under conditions of 5 DEG C after 29.25g potassium permanganate, reaction 3h, add 2mL hydrogen peroxide, obtain yellow mercury oxide,
Dried after yellow mercury oxide is filtered.The p-aminobenzene sulfonic acid for weighing 2g is dissolved in the sodium hydroxide solution that 15mL mass fractions are 2%,
P-aminobenzene sulfonic acid is pressed under conditions of 0 DEG C：The mass ratio of natrium nitrosum is 2:1 condition adds natrium nitrosum, by amino
Benzene sulfonic acid：The mol ratio 20 of hydrochloric acid:1 is added drop-wise to hydrochloric acid in solution, and white precipitate is made, and is dried after filtering.By obtained Huang
Color is precipitated and NaBH4In molar ratio 1:During 1.5 uniform mixing are fallen back, obtained white precipitate is pressed into white precipitate：Yellow
The mass ratio 1 of precipitation：1.2 are added to the water, and 6h is reacted under conditions of not higher than 0 DEG C, then into system by yellow mercury oxide：Hydration
The mol ratio 1 of hydrazine：1 adds hydrazine hydrate, and sulfonated graphene dispersion liquid is made.By obtained sulfonated graphene homogeneous dispersion drop coating
On ito glass, in 0.1mol/L MnSO4In the electrolyte of solution, using sulfonated graphene electrode as working electrode, Ag/AgCl
For reference electrode, platinum filament is, to electrode, to react 6min in 1.0V voltages at room temperature, obtain sulfonated graphene/manganese dioxide multiple
Composite electrode.0.05mol/L 3,4- ethene dioxythiophenes-styrene sulfonic acid is dissolved in 0.1mol/L Na2SO4In solution, as
Supporting electrolyte, using sulfonated graphene/manganese dioxide as working electrode, Ag/AgCl is reference electrode, and platinum filament is to electrode, room
6min is reacted in 1.0V voltages under temperature, sulfonated graphene/manganese dioxide/poly- is obtained（3,4- ethene dioxythiophenes）- polyphenyl second
Alkene sulfonic acid three-phase composite electrode.
A kind of vanadium cell of application three-phase composite electrode, including electrolyte, and the ionic membrane being placed in electrolyte, ionic membrane
Both sides are respectively equipped with electrode, electrode base insertion electrolyte.
Ionic membrane is multilayer material, and electroplating a layer thickness in the lower floor of cell nafion proton membrane one by pretreatment is
400nm silicon dioxide layer, then electroplate one layer of cell nafion proton membrane two in silicon dioxide layer lower floor.In cell nafion proton membrane
One layer of PDDA layer is electroplated in one upper surface, in the lower surface electricity of cell nafion proton membrane two
One layer of PSS layer of plating, that is, be made the ionic membrane with sandwich construction.
By analytically pure V2O3And V2O5According to 1：1 mass ratio uniformly after mixing, weighs 10g, adds to the 90% of 20mL
In concentrated sulfuric acid solution, be heated to reflux under conditions of 120 DEG C, naturally cool to after room temperature filter, obtain containing three, tetravalence vanadium from
The mixed electrolytic solution of son；Weigh 0.85g formic acid, 0.07g p-methyl benzenesulfonic acid, 1.46g 3- [3- (courage amido propyl) two
Methylamino] propane sulfonic acid inner salt is dissolved in redistilled water, be poured slowly into the state of at the uniform velocity stirring containing three, tetravalence vanadium from
The mixed electrolytic solution of son, is obtained containing the formic acid that mass fraction is 1.8%, 0.15% p-methyl benzenesulfonic acid and 3.1% 3- [3-
(courage amido propyl) dimethylamino] propane sulfonic acid inner salt mixed electrolytic solution.
Embodiment 3
The phosphorus pentoxide of the potassium peroxydisulfate and 1.5g that weigh 1g is dissolved in the concentrated sulfuric acid, 5g graphite is added, in 80 DEG C of bar
Under part, 4.3h is reacted, is cooled to after room temperature, filtered, dried, obtain solid A, solid A is mixed with 10mL 90% concentrated sulfuric acid
It is even, added under conditions of 2.7 DEG C after 29.25g potassium permanganate, reaction 2.5h, add 2mL hydrogen peroxide, obtain yellow
Precipitation, is dried after yellow mercury oxide is filtered.The p-aminobenzene sulfonic acid for weighing 2g is dissolved in the sodium hydroxide that 15mL mass fractions are 2%
Solution, presses p-aminobenzene sulfonic acid under conditions of 0 DEG C：The mass ratio of natrium nitrosum is 2:1 condition adds natrium nitrosum, by pair
Aminobenzenesulfonic acid：The mol ratio 20 of hydrochloric acid:1 is added drop-wise to hydrochloric acid in solution, and white precipitate is made, and is dried after filtering.It will be made
Yellow mercury oxide and NaBH4In molar ratio 1:During 1.5 uniform mixing are fallen back, obtained white precipitate is pressed into white precipitate：
The mass ratio 1 of yellow mercury oxide：1.2 are added to the water, and react 5.5h under conditions of not higher than 0 DEG C, then into system it is heavy by yellow
Form sediment：The mol ratio 1 of hydrazine hydrate：1 adds hydrazine hydrate, and sulfonated graphene dispersion liquid is made.By obtained sulfonated graphene dispersion liquid
Uniform drop coating is on ito glass, in 0.1mol/L MnSO4It is electric by work of sulfonated graphene electrode in the electrolyte of solution
Pole, Ag/AgCl is reference electrode, and platinum filament is, to electrode, to react 5.5min in 1.0V voltages at room temperature, obtain sulfonated graphite
Alkene/manganese dioxide composite electrode.0.05mol/L 3,4- ethene dioxythiophenes-styrene sulfonic acid is dissolved in 0.1mol/L
Na2SO4In solution, as supporting electrolyte, using sulfonated graphene/manganese dioxide as working electrode, Ag/AgCl is reference electrode,
Platinum filament is, to electrode, to react 5.5min in 1.0V voltages at room temperature, obtains sulfonated graphene/manganese dioxide/poly-（3,4- ethene
Dioxy thiophene）- polystyrolsulfon acid three-phase composite electrode.
A kind of vanadium cell of application three-phase composite electrode, including electrolyte, and the ionic membrane being placed in electrolyte, ionic membrane
Both sides are respectively equipped with electrode, electrode base insertion electrolyte.
Ionic membrane is multilayer material, and electroplating a layer thickness in the lower floor of cell nafion proton membrane one by pretreatment is
357nm silicon dioxide layer, then electroplate one layer of cell nafion proton membrane two in silicon dioxide layer lower floor.In cell nafion proton membrane
One layer of PDDA layer is electroplated in one upper surface, in the lower surface electricity of cell nafion proton membrane two
One layer of PSS layer of plating, that is, be made the ionic membrane with sandwich construction.
By analytically pure V2O3And V2O5According to 1：1 mass ratio uniformly after mixing, weighs 10g, adds to the 90% of 20mL
In concentrated sulfuric acid solution, be heated to reflux under conditions of 120 DEG C, naturally cool to after room temperature filter, obtain containing three, tetravalence vanadium from
The mixed electrolytic solution of son；Weigh 0.658g formic acid, 0.061g p-methyl benzenesulfonic acid, 1.316g 3- [3- (courage amido propyl)
Dimethylamino] propane sulfonic acid inner salt is dissolved in redistilled water, it is poured slowly into the state of at the uniform velocity stirring containing three, tetravalence vanadium
The mixed electrolytic solution of ion, is obtained containing the formic acid that mass fraction is 1.4%, 0.13% p-methyl benzenesulfonic acid and 2.8% 3- [3-
(courage amido propyl) dimethylamino] propane sulfonic acid inner salt mixed electrolytic solution.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (4)
1. a kind of three-phase composite electrode, it is characterised in that：By sulfonated graphene, manganese dioxide and poly-（3,4- ethylene dioxy thiophenes
Fen）- polystyrolsulfon acid is constituted；The manganese dioxide is plated on sulfonated graphene surface, described poly-（3,4- ethylene dioxy thiophenes
Fen）- polystyrolsulfon acid is plated on manganese dioxide layer surface.
2. a kind of three-phase composite electrode as claimed in claim 1, it is characterised in that made using following steps：
Step one：Weigh a certain amount of potassium peroxydisulfate and phosphorus pentoxide is dissolved in the concentrated sulfuric acid, graphite is added, in 80 DEG C of condition
Under, 4 ~ 5h is reacted, is cooled to after room temperature, is filtered, is dried, is obtained solid A, solid A is well mixed with the concentrated sulfuric acid, at 0 ~ 5 DEG C
Under conditions of in molar ratio be 1:1 adds after potassium permanganate, 2 ~ 3h of reaction, adds appropriate hydrogen peroxide, obtains yellow mercury oxide,
Dried after yellow mercury oxide is filtered；
Step 2：Weigh a certain amount of p-aminobenzene sulfonic acid and be dissolved in the sodium hydroxide solution that appropriate mass fraction is 2%, at 0 DEG C
Under conditions of press p-aminobenzene sulfonic acid：The mass ratio of natrium nitrosum is 2:1 condition adds natrium nitrosum, by p-aminophenyl sulphur
Acid：The mol ratio 20 of hydrochloric acid:1 is added drop-wise to hydrochloric acid in solution, and white precipitate is made, and is dried after filtering；
Step 3：By obtained yellow mercury oxide and NaBH in step one4In molar ratio 1:During 1.5 uniform mixing are fallen back, it will walk
Obtained white precipitate presses white precipitate in rapid two：The mass ratio 1 of yellow mercury oxide：1.2 it is added to the water, in not higher than 0 DEG C of bar
5 ~ 6h is reacted under part, then into system by yellow mercury oxide：The mol ratio 1 of hydrazine hydrate：1 adds hydrazine hydrate, and sulfonated graphene is made
Dispersion liquid；
Step 4：By obtained sulfonated graphene homogeneous dispersion drop coating is on ito glass in step 3, in 0.1mol/L
MnSO4In the electrolyte of solution, using sulfonated graphene electrode as working electrode, Ag/AgCl is reference electrode, and platinum filament is to electricity
Pole, 5 ~ 6min is reacted in 1.0V voltages, sulfonated graphene/manganese dioxide composite electrode is obtained at room temperature；
Step 5：0.05mol/L 3,4- ethene dioxythiophenes-styrene sulfonic acid is dissolved in 0.1mol/L Na2SO4In solution,
As supporting electrolyte, using sulfonated graphene/manganese dioxide as working electrode, Ag/AgCl is reference electrode, and platinum filament is to electricity
Pole, reacts 5 ~ 6min in 1.0V voltages at room temperature, obtains sulfonated graphene/manganese dioxide/poly-（3,4- ethene dioxythiophenes）-
Polystyrolsulfon acid three-phase composite electrode.
3. a kind of vanadium cell of application three-phase composite electrode as claimed in claim 1 or 2, it is characterised in that：Including electrolyte,
With the ionic membrane being placed in electrolyte, the ionic membrane both sides are respectively equipped with electrode, the electrode base insertion electrolyte；Institute
Ionic membrane is stated for multilayer material, the electrolyte is the V (III) comprising additive/V (IV) sulfuric acid solutions system mixing electrolysis
Liquid, the electrode is sulfonated graphene/manganese dioxide/poly-（3,4- ethene dioxythiophenes）- polystyrolsulfon acid three-phase composite electricity
Pole.
4. vanadium cell as claimed in claim 3, it is characterised in that：The ionic membrane includes cell nafion proton membrane one, described
The lower floor of cell nafion proton membrane one is covered with silicon dioxide layer, and the lower floor of the silica is covered with cell nafion proton membrane
Two；The thickness of the silicon dioxide layer is 300-400nm；The surface of cell nafion proton membrane one is covered with phthalic acid diethyl
Omega-diol diacrylate layer, the surface of cell nafion proton membrane two is covered with PSS layer；Include in the electrolyte
Mass fraction is 1.2 ~ 1.8% formic acid, 0.12 ~ 0.15% p-methyl benzenesulfonic acid and 2.5 ~ 3.1% 3- [3- (courage amido propyl)
Dimethylamino] propane sulfonic acid inner salt.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510681963.7A CN105336962B (en) | 2015-10-21 | 2015-10-21 | A kind of three-phase composite electrode of vanadium cell and preparation method thereof |
| CN201710623072.5A CN107248580B (en) | 2015-10-21 | 2015-10-21 | A kind of preparation method of three-phase composite electrode |
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| CN201510681963.7A CN105336962B (en) | 2015-10-21 | 2015-10-21 | A kind of three-phase composite electrode of vanadium cell and preparation method thereof |
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