CN105336962A - Three phase combination electrode of vanadium cells, and preparation method thereof - Google Patents
Three phase combination electrode of vanadium cells, and preparation method thereof Download PDFInfo
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- CN105336962A CN105336962A CN201510681963.7A CN201510681963A CN105336962A CN 105336962 A CN105336962 A CN 105336962A CN 201510681963 A CN201510681963 A CN 201510681963A CN 105336962 A CN105336962 A CN 105336962A
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Abstract
The invention discloses a three phase combination electrode, and belongs to the field of electrode. The three phase combination electrode is composed of sulfonated graphene, manganese dioxide, and manganese dioxide/poly(3,4-ethylenedioxythiophene)-polystyrolsulfon acid. The three phase combination electrode is capable of weakening etching of graphite electrodes, prolonging service life of vanadium cells, and improving application safety of vanadium cells.
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, is made up of battery pile, positive and negative electrolyte reservoir and other sub controlling unit.Vanadium cell is except possessing the feature of general redox flow batteries, and vanadium cell for battery plus-negative plate active material, eliminates the battery failure because electrolyte cross pollution causes with the vanadium ion solution of different valence state; Vanadium cell is being produced and substantially can not produced the material to human body and bad environmental in use procedure; The low price of vanadium cell simultaneously, energy efficiency is high, long service life, and reliability is high, and operation and maintenance expense is low, is a kind of outstanding energy-storage system.China is the country that vanadium resource enriches.Verified in the world in vanadium reserves, the occupancy volume of China occupies third place in the world; And the V of China at present
2o
5annual production reaches 2,101 ten thousand tons, occupies the 4th, the world.Development and utilization vanadium cell has special resources advantage in China.
The electrode of prior art vanadium cell all adopts graphite material, but positive pole side graphite cake exists etching phenomenon, easily causes battery leakage accident, causes the use of vanadium cell to there is serious potential safety hazard.
Summary of the invention
Goal of the invention of the present invention is: for above-mentioned Problems existing, provides a kind of etching phenomenon weakening graphite electrode, improves vanadium cell useful life, increases the three-phase composite electrode of the safety that vanadium cell uses.
The technical solution used in 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-rthylene dioxythiophene)-polystyrolsulfon acid composition.
Owing to adopting technique scheme, the special construction of Graphene makes it have high-specific surface area, high mechanical properties and high conductivity, but irreversible reunion easily occurs Graphene, and available active surface is greatly reduced, and its ratio capacitance is lower.Sulfonic functional Graphene, with high conductivity and surperficial high charged group, can improve the conductivity of electrode in the electrodes, intercept again the absorption of counter ion, thus improves current efficiency and desalination amount.It is high that manganese dioxide has specific volume, price is low, environment amenable feature, but the conductivity of manganese dioxide, mechanical stability is relatively poor, the conjugated structure of poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid makes it have good conductivity, has good invertibity and the conductivity of excellence.This three is carried out compound, utilize the synergy between each component, effectively can improve its cyclical stability and discharge and recharge invertibity, improve the combination property of electrode, avoid graphite cake in prior art and there is etching phenomenon, thus reduce the generation of battery leakage accident, greatly eliminate the potential safety hazard in the use procedure of vanadium cell.
A kind of three-phase composite electrode of the present invention, described manganese dioxide is plated on sulfonated graphene surface, and described poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid is plated on manganese dioxide layer surface.
A kind of three-phase composite electrode of the present invention, is characterized in that adopting following steps to make:
Step one: take a certain amount of potassium peroxydisulfate and phosphorus pentoxide is dissolved in the concentrated sulfuric acid, adds graphite, under the condition of 80 DEG C, reaction 4 ~ 5h, after being cooled to room temperature, filters, dry, obtain solid A, solid A is mixed with the concentrated sulfuric acid, in molar ratio for 1:1 adds potassium permanganate under the condition of 0 ~ 5 DEG C, after reaction 2 ~ 3h, add appropriate hydrogen peroxide, obtain yellow mercury oxide, dry after yellow mercury oxide is filtered;
Step 2: take a certain amount of sulfanilic acid and be dissolved in the sodium hydroxide solution that appropriate mass fraction is 2%, by sulfanilic acid under the condition of 0 DEG C: the mass ratio of natrium nitrosum is that the condition of 2:1 adds natrium nitrosum, by sulfanilic acid: hydrochloric acid is added drop-wise in solution by the mol ratio 20:1 of hydrochloric acid, obtained white precipitate, dry after filtering;
Step 3: by yellow mercury oxide obtained in step one and NaBH
4during 1:1.5 Homogeneous phase mixing is fallen back in molar ratio, by the white precipitate obtained in step 2 in mass ratio 1:1.2 be added to the water, 5 ~ 6h is reacted under not higher than the condition of 0 DEG C, again in system by yellow mercury oxide: the mol ratio 1:1 of hydrazine hydrate adds hydrazine hydrate, obtained sulfonated graphene dispersion liquid;
Step 4: the sulfonated graphene homogeneous dispersion obtained in step 3 is dripped and is coated on ito glass, at 0.1mol/LMnSO
4in the electrolyte of solution, with sulfonated graphene electrode for work electrode, Ag/AgCl is reference electrode, and platinum filament is to electrode, reacts 5 ~ 6min, obtain sulfonated graphene/manganese dioxide composite electrode under room temperature in 1.0V voltage;
Step 5: the 3,4-rthylene dioxythiophene-styrene sulfonic acid of 0.05mol/L is dissolved in 0.1mol/LNa
2sO
4in solution, as supporting electrolyte, with sulfonated graphene/manganese dioxide for work electrode, Ag/AgCl is reference electrode, platinum filament is to electrode, in 1.0V voltage, react 5 ~ 6min under room temperature, obtain sulfonated graphene/manganese dioxide/poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid three-phase composite electrode.
Apply a vanadium cell for three-phase composite electrode of the present invention, comprise electrolyte, and be placed in the ionic membrane in electrolyte, described ionic membrane both sides are respectively equipped with electrode, and described electrode base inserts in electrolyte; Described ionic membrane is multilayer material, described electrolyte is V (III)/V (IV) the sulfuric acid solution system mixed electrolytic solution comprising additive, described electrode is sulfonated graphene/manganese dioxide/poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid three-phase composite electrode.
Owing to have employed technique scheme, the ionic membrane of prior art is improved, not only ensure the know clearly proton conductivity of ionic membrane, chemical stability, thermal stability and mechanical performance, reduce vanadium ion permeability simultaneously, substantially increase the energy efficiency of battery; Adopting graphene combination electrode, there is etching phenomenon in the electrode solving vanadium cell in prior art; The improvement of electrolyte is improve to the invertibity of electrode reaction, improve the stability of electrolyte, decrease the appearance of vanadium ion crystallization, improve energy content of battery efficiency.
Apply a vanadium cell for three-phase composite electrode, described ionic membrane comprises cell nafion proton membrane one, and the lower floor of described cell nafion proton membrane one is coated with silicon dioxide layer, and the lower floor of described silicon dioxide is coated with cell nafion proton membrane two; The thickness of described silicon dioxide layer is 300-400nm; Described cell nafion proton membrane one surface is covered with PDDA layer, and described cell nafion proton membrane two surface is covered with PSS layer; The formic acid that mass fraction is 1.2 ~ 1.8% is included, the p-methyl benzenesulfonic acid of 0.12 ~ 0.15% and 3-[3-(courage amido propyl) dimethylamino] the propane sulfonic acid inner salt of 2.5 ~ 3.1% in described electrolyte.
Owing to have employed technique scheme, PDDA layer and PSS layer can realize being cross-linked sulfonic acid group in cell nafion proton membrane, the water content of film is improve while reducing vanadium ion permeability, proton is more easily freely passed through, further increase proton conductivity and the energy efficiency of ionic membrane, p-methyl benzenesulfonic acid can improve the invertibity of electrode process, reduces electrochemistry polarity, helpful to raising energy content of battery efficiency; The viscosity of negative electrode solution can be reduced, reduce the kinetic energy loss of pump and reduce the resistance to mass tranfer of electrode process, but p-methyl benzenesulfonic acid also can reduce the conductivity of negative electrode solution, increases the internal resistance of cell; Formic acid improves the stability of mixed electrolytic solution, has good stabilization to trivalent and tetravalent vanadium ion, improves the chemical property of electrolyte and the reactivity of electrolyte, thus weakens the impact of p-methyl benzenesulfonic acid on conductivity; 3-[3-(courage amido propyl) dimethylamino] propane sulfonic acid inner salt is zwitterionic surfactant, improves the solubility of vanadium ion, decreases crystallization in electrolyte and occurs, improve the invertibity of electrode reaction, also well improve V simultaneously
4+thermal stability.
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows:
1, electrode cycle stability and discharge and recharge invertibity is effectively improved, improve the combination property of electrode, avoid graphite cake in prior art and there is etching phenomenon, thus reduce the generation of battery leakage accident, greatly eliminate the potential safety hazard in the use procedure of vanadium cell.
2, make vanadium permeability greatly reduce, but passing through of proton can not be affected, ensure that the proton conductivity of ionic membrane, improve the energy efficiency of battery, improve the invertibity of electrode reaction, improve the stability of electrolyte, decrease the appearance of vanadium ion crystallization, add V
4+the thermal stability of ion.
Embodiment
The present invention is described in detail below.
In order to make the object of invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The phosphorus pentoxide of the potassium peroxydisulfate and 1.5g that take 1g is dissolved in the concentrated sulfuric acid, adds 5g graphite, under the condition of 80 DEG C, reaction 4h, after being cooled to room temperature, filters, dry, obtain solid A, 90% concentrated sulfuric acid of solid A and 10mL is mixed, under the condition of 0 DEG C, adds the potassium permanganate of 29.25g, after reaction 2h, add the hydrogen peroxide of 2mL, obtain yellow mercury oxide, dry after yellow mercury oxide is filtered.The sulfanilic acid taking 2g is dissolved in the sodium hydroxide solution that 15mL mass fraction is 2%, by sulfanilic acid under the condition of 0 DEG C: the mass ratio of natrium nitrosum is that the condition of 2:1 adds natrium nitrosum, by sulfanilic acid: hydrochloric acid is added drop-wise in solution by the mol ratio 20:1 of hydrochloric acid, obtained white precipitate, dry after filtering.By obtained yellow mercury oxide and NaBH
4during 1:1.5 Homogeneous phase mixing is fallen back in molar ratio, by obtained white precipitate by white precipitate: the mass ratio 1:1.2 of yellow mercury oxide is added to the water, 5h is reacted under not higher than the condition of 0 DEG C, again in system by yellow mercury oxide: the mol ratio 1:1 of hydrazine hydrate adds hydrazine hydrate, obtained sulfonated graphene dispersion liquid.Being dripped by obtained sulfonated graphene homogeneous dispersion is coated on ito glass, at 0.1mol/LMnSO
4in the electrolyte of solution, with sulfonated graphene electrode for work electrode, Ag/AgCl is reference electrode, and platinum filament is to electrode, reacts 5min under room temperature in 1.0V voltage, obtains sulfonated graphene/manganese dioxide composite electrode.3,4-rthylene dioxythiophene-the styrene sulfonic acid of 0.05mol/L is dissolved in 0.1mol/LNa
2sO
4in solution, as supporting electrolyte, with sulfonated graphene/manganese dioxide for work electrode, Ag/AgCl is reference electrode, platinum filament is to electrode, in 1.0V voltage, react 5min under room temperature, obtain sulfonated graphene/manganese dioxide/poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid three-phase composite electrode.
Apply a vanadium cell for three-phase composite electrode, comprise electrolyte, and be placed in the ionic membrane in electrolyte, ionic membrane both sides are respectively equipped with electrode, and electrode base inserts in electrolyte.
Ionic membrane is multilayer material, is electroplating the silicon dioxide layer that a layer thickness is 300nm, then electroplate one deck cell nafion proton membrane two in silicon dioxide layer lower floor through pretreated cell nafion proton membrane one lower floor.Electroplate one deck PDDA layer at the upper surface of cell nafion proton membrane one, electroplate one deck PSS layer at the lower surface of cell nafion proton membrane two, namely make the ionic membrane with sandwich construction.
By analytically pure V
2o
3and V
2o
5according to the quality of 1:1 than after Homogeneous phase mixing, take 10g, be added in 90% concentrated sulfuric acid solution of 20mL, under the condition of 120 DEG C, add hot reflux, filter after naturally cooling to room temperature, obtain containing three, the mixed electrolytic solution of tetravalent vanadium ion; Take the formic acid of 0.56g, the p-methyl benzenesulfonic acid of 0.056g, 3-[3-(courage amido propyl) dimethylamino] the propane sulfonic acid inner salt of 1.16g is dissolved in redistilled water, slowly pour into containing three under the state at the uniform velocity stirred, the mixed electrolytic solution of tetravalent vanadium ion, obtaining containing mass fraction is the formic acid of 1.2%, the mixed electrolytic solution of the p-methyl benzenesulfonic acid of 0.12% and 3-[3-(courage amido propyl) dimethylamino] the propane sulfonic acid inner salt of 2.5%.
Embodiment 2
The phosphorus pentoxide of the potassium peroxydisulfate and 1.5g that take 1g is dissolved in the concentrated sulfuric acid, adds 5g graphite, under the condition of 80 DEG C, reaction 5h, after being cooled to room temperature, filters, dry, obtain solid A, 90% concentrated sulfuric acid of solid A and 10mL is mixed, under the condition of 5 DEG C, adds the potassium permanganate of 29.25g, after reaction 3h, add the hydrogen peroxide of 2mL, obtain yellow mercury oxide, dry after yellow mercury oxide is filtered.The sulfanilic acid taking 2g is dissolved in the sodium hydroxide solution that 15mL mass fraction is 2%, by sulfanilic acid under the condition of 0 DEG C: the mass ratio of natrium nitrosum is that the condition of 2:1 adds natrium nitrosum, by sulfanilic acid: hydrochloric acid is added drop-wise in solution by the mol ratio 20:1 of hydrochloric acid, obtained white precipitate, dry after filtering.By obtained yellow mercury oxide and NaBH
4during 1:1.5 Homogeneous phase mixing is fallen back in molar ratio, by obtained white precipitate by white precipitate: the mass ratio 1:1.2 of yellow mercury oxide is added to the water, 6h is reacted under not higher than the condition of 0 DEG C, again in system by yellow mercury oxide: the mol ratio 1:1 of hydrazine hydrate adds hydrazine hydrate, obtained sulfonated graphene dispersion liquid.Being dripped by obtained sulfonated graphene homogeneous dispersion is coated on ito glass, at 0.1mol/LMnSO
4in the electrolyte of solution, with sulfonated graphene electrode for work electrode, Ag/AgCl is reference electrode, and platinum filament is to electrode, reacts 6min under room temperature in 1.0V voltage, obtains sulfonated graphene/manganese dioxide composite electrode.3,4-rthylene dioxythiophene-the styrene sulfonic acid of 0.05mol/L is dissolved in 0.1mol/LNa
2sO
4in solution, as supporting electrolyte, with sulfonated graphene/manganese dioxide for work electrode, Ag/AgCl is reference electrode, platinum filament is to electrode, in 1.0V voltage, react 6min under room temperature, obtain sulfonated graphene/manganese dioxide/poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid three-phase composite electrode.
Apply a vanadium cell for three-phase composite electrode, comprise electrolyte, and be placed in the ionic membrane in electrolyte, ionic membrane both sides are respectively equipped with electrode, and electrode base inserts in electrolyte.
Ionic membrane is multilayer material, is electroplating the silicon dioxide layer that a layer thickness is 400nm, then electroplate one deck cell nafion proton membrane two in silicon dioxide layer lower floor through pretreated cell nafion proton membrane one lower floor.Electroplate one deck PDDA layer at the upper surface of cell nafion proton membrane one, electroplate one deck PSS layer at the lower surface of cell nafion proton membrane two, namely make the ionic membrane with sandwich construction.
By analytically pure V
2o
3and V
2o
5according to the quality of 1:1 than after Homogeneous phase mixing, take 10g, be added in 90% concentrated sulfuric acid solution of 20mL, under the condition of 120 DEG C, add hot reflux, filter after naturally cooling to room temperature, obtain containing three, the mixed electrolytic solution of tetravalent vanadium ion; Take the formic acid of 0.85g, the p-methyl benzenesulfonic acid of 0.07g, 3-[3-(courage amido propyl) dimethylamino] the propane sulfonic acid inner salt of 1.46g is dissolved in redistilled water, slowly pour into containing three under the state at the uniform velocity stirred, the mixed electrolytic solution of tetravalent vanadium ion, obtaining containing mass fraction is the formic acid of 1.8%, the mixed electrolytic solution of the p-methyl benzenesulfonic acid of 0.15% and 3-[3-(courage amido propyl) dimethylamino] the propane sulfonic acid inner salt of 3.1%.
Embodiment 3
The phosphorus pentoxide of the potassium peroxydisulfate and 1.5g that take 1g is dissolved in the concentrated sulfuric acid, adds 5g graphite, under the condition of 80 DEG C, reaction 4.3h, after being cooled to room temperature, filters, dry, obtain solid A, 90% concentrated sulfuric acid of solid A and 10mL is mixed, under the condition of 2.7 DEG C, adds the potassium permanganate of 29.25g, after reaction 2.5h, add the hydrogen peroxide of 2mL, obtain yellow mercury oxide, dry after yellow mercury oxide is filtered.The sulfanilic acid taking 2g is dissolved in the sodium hydroxide solution that 15mL mass fraction is 2%, by sulfanilic acid under the condition of 0 DEG C: the mass ratio of natrium nitrosum is that the condition of 2:1 adds natrium nitrosum, by sulfanilic acid: hydrochloric acid is added drop-wise in solution by the mol ratio 20:1 of hydrochloric acid, obtained white precipitate, dry after filtering.By obtained yellow mercury oxide and NaBH
4during 1:1.5 Homogeneous phase mixing is fallen back in molar ratio, by obtained white precipitate by white precipitate: the mass ratio 1:1.2 of yellow mercury oxide is added to the water, 5.5h is reacted under not higher than the condition of 0 DEG C, again in system by yellow mercury oxide: the mol ratio 1:1 of hydrazine hydrate adds hydrazine hydrate, obtained sulfonated graphene dispersion liquid.Being dripped by obtained sulfonated graphene homogeneous dispersion is coated on ito glass, at 0.1mol/LMnSO
4in the electrolyte of solution, with sulfonated graphene electrode for work electrode, Ag/AgCl is reference electrode, and platinum filament is to electrode, reacts 5.5min under room temperature in 1.0V voltage, obtains sulfonated graphene/manganese dioxide composite electrode.3,4-rthylene dioxythiophene-the styrene sulfonic acid of 0.05mol/L is dissolved in 0.1mol/LNa
2sO
4in solution, as supporting electrolyte, with sulfonated graphene/manganese dioxide for work electrode, Ag/AgCl is reference electrode, platinum filament is to electrode, in 1.0V voltage, react 5.5min under room temperature, obtain sulfonated graphene/manganese dioxide/poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid three-phase composite electrode.
Apply a vanadium cell for three-phase composite electrode, comprise electrolyte, and be placed in the ionic membrane in electrolyte, ionic membrane both sides are respectively equipped with electrode, and electrode base inserts in electrolyte.
Ionic membrane is multilayer material, is electroplating the silicon dioxide layer that a layer thickness is 357nm, then electroplate one deck cell nafion proton membrane two in silicon dioxide layer lower floor through pretreated cell nafion proton membrane one lower floor.Electroplate one deck PDDA layer at the upper surface of cell nafion proton membrane one, electroplate one deck PSS layer at the lower surface of cell nafion proton membrane two, namely make the ionic membrane with sandwich construction.
By analytically pure V
2o
3and V
2o
5according to the quality of 1:1 than after Homogeneous phase mixing, take 10g, be added in 90% concentrated sulfuric acid solution of 20mL, under the condition of 120 DEG C, add hot reflux, filter after naturally cooling to room temperature, obtain containing three, the mixed electrolytic solution of tetravalent vanadium ion; Take the formic acid of 0.658g, the p-methyl benzenesulfonic acid of 0.061g, 3-[3-(courage amido propyl) dimethylamino] the propane sulfonic acid inner salt of 1.316g is dissolved in redistilled water, slowly pour into containing three under the state at the uniform velocity stirred, the mixed electrolytic solution of tetravalent vanadium ion, obtaining containing mass fraction is the formic acid of 1.4%, the mixed electrolytic solution of the p-methyl benzenesulfonic acid of 0.13% and 3-[3-(courage amido propyl) dimethylamino] the propane sulfonic acid inner salt of 2.8%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. a three-phase composite electrode, is characterized in that: by sulfonated graphene, manganese dioxide and manganese dioxide/poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid composition.
2. a kind of three-phase composite electrode as claimed in claim 1, is characterized in that: described manganese dioxide is plated on sulfonated graphene surface, and described poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid is plated on manganese dioxide layer surface.
3. a kind of three-phase composite electrode as claimed in claim 1 or 2, is characterized in that adopting following steps to make:
Step one: take a certain amount of potassium peroxydisulfate and phosphorus pentoxide is dissolved in the concentrated sulfuric acid, adds graphite, under the condition of 80 DEG C, reaction 4 ~ 5h, after being cooled to room temperature, filters, dry, obtain solid A, solid A is mixed with the concentrated sulfuric acid, in molar ratio for 1:1 adds potassium permanganate under the condition of 0 ~ 5 DEG C, after reaction 2 ~ 3h, add appropriate hydrogen peroxide, obtain yellow mercury oxide, dry after yellow mercury oxide is filtered;
Step 2: take a certain amount of sulfanilic acid and be dissolved in the sodium hydroxide solution that appropriate mass fraction is 2%, by sulfanilic acid under the condition of 0 DEG C: the mass ratio of natrium nitrosum is that the condition of 2:1 adds natrium nitrosum, by sulfanilic acid: hydrochloric acid is added drop-wise in solution by the mol ratio 20:1 of hydrochloric acid, obtained white precipitate, dry after filtering;
Step 3: by yellow mercury oxide obtained in step one and NaBH
4during 1:1.5 Homogeneous phase mixing is fallen back in molar ratio, by the white precipitate obtained in step 2 in mass ratio 1:1.2 be added to the water, 5 ~ 6h is reacted under not higher than the condition of 0 DEG C, again in system by yellow mercury oxide: the mol ratio 1:1 of hydrazine hydrate adds hydrazine hydrate, obtained sulfonated graphene dispersion liquid;
Step 4: the sulfonated graphene homogeneous dispersion obtained in step 3 is dripped and is coated on ito glass, at 0.1mol/LMnSO
4in the electrolyte of solution, with sulfonated graphene electrode for work electrode, Ag/AgCl is reference electrode, and platinum filament is to electrode, reacts 5 ~ 6min, obtain sulfonated graphene/manganese dioxide composite electrode under room temperature in 1.0V voltage;
Step 5: the 3,4-rthylene dioxythiophene-styrene sulfonic acid of 0.05mol/L is dissolved in 0.1mol/LNa
2sO
4in solution, as supporting electrolyte, with sulfonated graphene/manganese dioxide for work electrode, Ag/AgCl is reference electrode, platinum filament is to electrode, in 1.0V voltage, react 5 ~ 6min under room temperature, obtain sulfonated graphene/manganese dioxide/poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid three-phase composite electrode.
4. a vanadium cell for the three-phase composite electrode of application as described in claim 1-3, it is characterized in that: comprise electrolyte, and be placed in the ionic membrane in electrolyte, described ionic membrane both sides are respectively equipped with electrode, and described electrode base inserts in electrolyte; Described ionic membrane is multilayer material, described electrolyte is V (III)/V (IV) the sulfuric acid solution system mixed electrolytic solution comprising additive, described electrode is sulfonated graphene/manganese dioxide/poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid three-phase composite electrode.
5. a kind of vanadium cell applying three-phase composite electrode as claimed in claim 4, it is characterized in that: described ionic membrane comprises cell nafion proton membrane one, the lower floor of described cell nafion proton membrane one is coated with silicon dioxide layer, and the lower floor of described silicon dioxide is coated with cell nafion proton membrane two; The thickness of described silicon dioxide layer is 300-400nm; Described cell nafion proton membrane one surface is covered with PDDA layer, and described cell nafion proton membrane two surface is covered with PSS layer; The formic acid that mass fraction is 1.2 ~ 1.8% is included, the p-methyl benzenesulfonic acid of 0.12 ~ 0.15% and 3-[3-(courage amido propyl) dimethylamino] the propane sulfonic acid inner salt of 2.5 ~ 3.1% in described electrolyte.
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| CN106960973A (en) * | 2015-10-21 | 2017-07-18 | 成都九十度工业产品设计有限公司 | A kind of preparation method of the three-phase composite electrode of vanadium cell |
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| WO2006005466A1 (en) * | 2004-07-08 | 2006-01-19 | Sartorius Ag | Gas diffusion electrodes, method for the production of gas diffusion electrodes and fuel cells using said gas diffusion electrodes |
| CN103098263A (en) * | 2010-09-09 | 2013-05-08 | 加州理工学院 | Electrochemical energy storage systems and methods |
| CN103503201A (en) * | 2010-12-16 | 2014-01-08 | 24M技术公司 | High energy density redox flow device |
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| CN104868141B (en) * | 2015-05-06 | 2017-05-31 | 苏州高通新材料科技有限公司 | Sulfonated graphene and perfluorinated sulfonic resin compound proton exchange membrane and preparation method thereof |
| CN106960973B (en) * | 2015-10-21 | 2019-10-25 | 成都九十度工业产品设计有限公司 | A kind of preparation method of the three-phase composite electrode of vanadium cell |
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| WO2006005466A1 (en) * | 2004-07-08 | 2006-01-19 | Sartorius Ag | Gas diffusion electrodes, method for the production of gas diffusion electrodes and fuel cells using said gas diffusion electrodes |
| CN103098263A (en) * | 2010-09-09 | 2013-05-08 | 加州理工学院 | Electrochemical energy storage systems and methods |
| CN103503201A (en) * | 2010-12-16 | 2014-01-08 | 24M技术公司 | High energy density redox flow device |
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| CN106960973A (en) * | 2015-10-21 | 2017-07-18 | 成都九十度工业产品设计有限公司 | A kind of preparation method of the three-phase composite electrode of vanadium cell |
| CN106960973B (en) * | 2015-10-21 | 2019-10-25 | 成都九十度工业产品设计有限公司 | A kind of preparation method of the three-phase composite electrode of vanadium cell |
| CN106757128A (en) * | 2016-11-30 | 2017-05-31 | 彭州市运达知识产权服务有限公司 | A kind of indoor oxygenation device |
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| CN107248580A (en) | 2017-10-13 |
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