CN105448531A - Method for preparing needle-like manganese dioxide/graphene composite electrode material - Google Patents
Method for preparing needle-like manganese dioxide/graphene composite electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
Disclosed is a method for preparing a needle-like manganese dioxide/graphene composite electrode material. The invention relates to a method for preparing a composite electrode material, and aims to solve the problem that the use of binder or conductive adhesive in the existing composite electrode material preparation process results in a complex technology and high cost of preparation, and the improvement of the electrochemical performance of the electrode material depends on the control of the amount and morphology of metal oxide. The method of the invention comprises the following steps: placing a conductive material in a plasma enhanced chemical vapor deposition vacuum device, and carrying out graphene deposition and etching to get an etched graphene substrate material; and then, putting the graphene substrate material as a positive electrode and a platinum sheet as a negative electrode in electrolyte for deposition. The method of the invention is used for preparing the needle-like manganese dioxide/graphene composite electrode material.
Description
Technical field
The present invention relates to the preparation method of combination electrode material.
Background technology
Along with the progress of human society, the demand of the energy is rapidly increased.Ultracapacitor has the high specific power of traditional capacitor and the high specific energy of battery concurrently, thus has broad application prospects.Develop electrode material for super capacitor prepared by a kind of high-energy-density and power density, long circulation life, low cost extremely urgent.
Current electrode material mainly concentrates on two kinds: wherein double electric layer capacitor is widely used is various material with carbon elements, be characterized in that conductance is high, specific area is large, cyclicity is good, but its ratio capacitance is lower; Another kind of, be the metal oxide materials being used as fake capacitance, ratio capacitance is generally higher, but the problem that existence and stability is poor.If employing combination electrode, just can draw the advantage of the two, reach better capacitive properties.But prepared that combination electrode material is many can use binding agent or conducting resinl etc., complex process in the past, improve preparation cost, and the control of the quantity of metal oxide and pattern had a great impact for its fake capacitance characteristic.
Summary of the invention
The present invention will solve in existing combination electrode material preparation process and use binding agent or conducting resinl etc., complex process, preparation cost is high, and the problem of the chemical property of electrode material is improved by the quantity and pattern controlling metal oxide, and the preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material is provided.
A preparation method for needle-like manganese dioxide/graphene combination electrode material, specifically carries out according to following steps:
One, electric conducting material is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, pass into hydrogen, hydrogen gas flow is regulated to be 10sccm ~ 50sccm, pressure in plasma enhanced chemical vapor deposition vacuum plant is regulated to be 150Pa ~ 350Pa, and under pressure is 150Pa ~ 350Pa and hydrogen atmosphere, by temperature most 500 DEG C ~ 700 DEG C in 20min ~ 60min;
Two, argon gas and methane gas is passed into, the gas flow regulating methane is 35sccm ~ 45sccm, the gas flow regulating argon gas is 80sccm ~ 100sccm, pressure in plasma enhanced chemical vapor deposition vacuum plant is regulated to be 300Pa ~ 500Pa, then radio-frequency power be 100W ~ 200W, pressure deposits under be 300Pa ~ 500Pa and temperature being the condition of 500 DEG C ~ 700 DEG C, sedimentation time is 20min ~ 35min;
Three, after deposition terminates, stop passing into methane gas, adjustment argon flow amount is 20sccm ~ 80sccm, pressure in plasma enhanced chemical vapor deposition vacuum plant is regulated to be 100Pa ~ 400Pa, then argon gas atmosphere, pressure be 100Pa ~ 400Pa, under radio-frequency power be 75W ~ 225W and temperature is the condition of 500 DEG C ~ 700 DEG C, etching 30s ~ 10min;
Four, after etching terminates, with cooling rate be 5 DEG C/s ~ 20 DEG C/s, be 500 DEG C ~ 700 DEG C from temperature and be cooled to room temperature, take out, obtain the graphene substrate material after etching;
Five, with the graphene substrate material after etching for positive pole, take platinized platinum as negative pole, graphene substrate material positive pole after etching and platinized platinum negative pole are put into electrolyte, and then applying constant current at positive pole and negative pole both sides, is 0.5mA/cm in the current density of constant current
2~ 50mA/cm
2lower deposition 1min ~ 60min, deposits rear washed with de-ionized water, and to be placed in temperature be that the baking box of 80 DEG C ~ 120 DEG C dries 30min ~ 120min, namely completes the preparation method of needle-like manganese dioxide/graphene combination electrode material;
The metabisulfite solution of described electrolyte to be concentration be 0.1mol/L ~ 0.3mol/L and concentration are the mixed solution of the manganese sulfate solution of 0.1mol/L ~ 0.3mol/L; The volume ratio of described concentration to be the metabisulfite solution of 0.1mol/L ~ 0.3mol/L and concentration the be manganese sulfate solution of 0.1mol/L ~ 0.3mol/L is 1:1.
Conductive substrates of the present invention is under the acting in conjunction of argon gas and methane, by plasma discharge effect, prepare orthotropic superior in quality Graphene, again by argon gas ionization, surface etch is carried out with argon ion bombardment Graphene, then as substrate, the mode of constant current electrochemical deposition is adopted to prepare needle-like manganese dioxide/graphene composite material, pass through preferred parameter, be conducive to the formation of the manganese dioxide of acicular texture, and can by changing the density, size etc. of the manganese dioxide of corresponding parameter adjustment acicular texture.
The invention has the beneficial effects as follows:
1. the present invention is by the method for electrochemical deposition, adopt constant current electro-deposition, orthotropic Graphene generates the manganese dioxide of needle-like, introduce redox reaction and the fake capacitance energy storage behavior produced, form combination electrode material, than the electrode material of single pure phase, there is better capacitance characteristic, have broad application prospects.
2. the manganese dioxide of needle-like has open structure, not only adds the specific area of material, makes electrode material have more energy storage regions, the rapid movement of favourable electric charge; Nor the Graphene of bottom can be covered completely and make it directly cannot contact with electrolyte, there is good permeability, the three-dimensional of Graphene is retained to greatest extent without the advantage of stacked structure.And while the manganese dioxide of needle-like remains Graphene good electric conductivity, improve the ratio capacitance value of electrode material, improve the cyclical stability of self simultaneously, and surface-treated Graphene and manganese dioxide have better associativity, make combination electrode material cyclical stability more stable, the combination electrode material that the present invention obtains is through 10
4after secondary charge-discharge test, ratio capacitance value is still left original more than 90%.
3. before electrochemical deposition manganese dioxide, to graphenic surface preliminary treatment-carry out Ar etching, the Sheet Graphite alkene that Ar atom bombardment is vertical can introduce defect at its top and sidewall, improve the wetability of material, the contact area of electrolyte increases, and meanwhile, the raising of degree of imperfection has activated the chemical property of Graphene, room, dangling bonds and amorphous carbon etc. more easily catch MnO
2initial forming core, makes deposition process easier, adds Graphene and MnO
2between adhesion, improve the cyclical stability of combination electrode.
4. method of the present invention is simple, and efficiently, low cost, is convenient to suitability for industrialized production, and the quality preparing needle-like manganese dioxide/graphene combination electrode material is high, has a good application prospect in electrode material for super capacitor.
The present invention is used for a kind of preparation method of needle-like manganese dioxide/graphene combination electrode material.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of needle-like manganese dioxide/graphene combination electrode material prepared by embodiment one;
Fig. 2 is the cyclic voltammetry curve of needle-like manganese dioxide/graphene combination electrode material prepared by embodiment one.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material described in present embodiment, specifically carry out according to following steps:
One, electric conducting material is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, pass into hydrogen, hydrogen gas flow is regulated to be 10sccm ~ 50sccm, pressure in plasma enhanced chemical vapor deposition vacuum plant is regulated to be 150Pa ~ 350Pa, and under pressure is 150Pa ~ 350Pa and hydrogen atmosphere, by temperature most 500 DEG C ~ 700 DEG C in 20min ~ 60min;
Two, argon gas and methane gas is passed into, the gas flow regulating methane is 35sccm ~ 45sccm, the gas flow regulating argon gas is 80sccm ~ 100sccm, pressure in plasma enhanced chemical vapor deposition vacuum plant is regulated to be 300Pa ~ 500Pa, then radio-frequency power be 100W ~ 200W, pressure deposits under be 300Pa ~ 500Pa and temperature being the condition of 500 DEG C ~ 700 DEG C, sedimentation time is 20min ~ 35min;
Three, after deposition terminates, stop passing into methane gas, adjustment argon flow amount is 20sccm ~ 80sccm, pressure in plasma enhanced chemical vapor deposition vacuum plant is regulated to be 100Pa ~ 400Pa, then argon gas atmosphere, pressure be 100Pa ~ 400Pa, under radio-frequency power be 75W ~ 225W and temperature is the condition of 500 DEG C ~ 700 DEG C, etching 30s ~ 10min;
Four, after etching terminates, with cooling rate be 5 DEG C/s ~ 20 DEG C/s, be 500 DEG C ~ 700 DEG C from temperature and be cooled to room temperature, take out, obtain the graphene substrate material after etching;
Five, with the graphene substrate material after etching for positive pole, take platinized platinum as negative pole, graphene substrate material positive pole after etching and platinized platinum negative pole are put into electrolyte, and then applying constant current at positive pole and negative pole both sides, is 0.5mA/cm in the current density of constant current
2~ 50mA/cm
2lower deposition 1min ~ 60min, deposits rear washed with de-ionized water, and to be placed in temperature be that the baking box of 80 DEG C ~ 120 DEG C dries 30min ~ 120min, namely completes the preparation method of needle-like manganese dioxide/graphene combination electrode material;
The metabisulfite solution of described electrolyte to be concentration be 0.1mol/L ~ 0.3mol/L and concentration are the mixed solution of the manganese sulfate solution of 0.1mol/L ~ 0.3mol/L; The volume ratio of described concentration to be the metabisulfite solution of 0.1mol/L ~ 0.3mol/L and concentration the be manganese sulfate solution of 0.1mol/L ~ 0.3mol/L is 1:1.
The beneficial effect of present embodiment is:
1. present embodiment is by the method for electrochemical deposition, adopt constant current electro-deposition, orthotropic Graphene generates the manganese dioxide of needle-like, introduce redox reaction and the fake capacitance energy storage behavior produced, form combination electrode material, than the electrode material of single pure phase, there is better capacitance characteristic, have broad application prospects.
2. the manganese dioxide of needle-like has open structure, not only adds the specific area of material, makes electrode material have more energy storage regions, the rapid movement of favourable electric charge; Nor the Graphene of bottom can be covered completely and make it directly cannot contact with electrolyte, there is good permeability, the three-dimensional of Graphene is retained to greatest extent without the advantage of stacked structure.And while the manganese dioxide of needle-like remains Graphene good electric conductivity, improve the ratio capacitance value of electrode material, improve the cyclical stability of self simultaneously, and surface-treated Graphene and manganese dioxide have better associativity, make combination electrode material cyclical stability more stable, the combination electrode material that the present invention obtains is through 10
4after secondary charge-discharge test, ratio capacitance value is still left original more than 90%.
3. before electrochemical deposition manganese dioxide, to graphenic surface preliminary treatment-carry out Ar etching, the Sheet Graphite alkene that Ar atom bombardment is vertical can introduce defect at its top and sidewall, improve the wetability of material, the contact area of electrolyte increases, and meanwhile, the raising of degree of imperfection has activated the chemical property of Graphene, room, dangling bonds and amorphous carbon etc. more easily catch MnO
2initial forming core, makes deposition process easier, adds Graphene and MnO
2between adhesion, improve the cyclical stability of combination electrode.
4. the method for present embodiment is simple, and efficiently, low cost, is convenient to suitability for industrialized production, and the quality preparing needle-like manganese dioxide/graphene combination electrode material is high, has a good application prospect in electrode material for super capacitor.
The present invention proposes to utilize the method for electrochemical deposition on orthotropic Graphene, prepare needle-like manganese dioxide/graphene combination electrode material.Graphene conductivity is high, and specific area is large, and stable electrochemical property is the desirable carbon-based supports preparing the electrode material of high-performance super capacitor with metal oxide compound; And manganese dioxide has rich reserves, cheap, environmental friendliness, ratio capacitance is high comparatively.MnO
2have different morphologies structure, often kind of appearance structure is very large to its Electrochemical Performances.The MnO of needle-like
2there is open structure, add the specific area of material on the one hand, make electrode material have more energy storage regions, for the accumulation of electric charge and transmission provide more multipath; Also the orthotropic Graphene of bottom can not be covered completely on the other hand makes it directly cannot contact with electrolyte, has good permeability, the three-dimensional of vertical-growth Graphene is retained to greatest extent without the advantage of stacked structure.Simultaneously due to MnO
2have splendid hydrophily, electrolyte can be fully wetting and through MnO in electrode material surface
2needle-like layer directly contacts with Graphene, and Graphene then improves the cyclical stability of manganese dioxide.The electrochemical deposition manganese dioxide mentioned in the present invention directly prepares MnO on orthotropic Graphene
2, can directly by the current density of regulation and control electrolytic cell, the species composition of electrolysis time and electrolyte and concentration, the state modulator MnO such as pH value
2growth; Consider the nonwetting property of Graphene for water-soluble electrolyte and the stability of its chemical property, before carrying out chemical deposition, first Ar etching is carried out to Graphene, the Sheet Graphite alkene that Ar atom bombardment is vertical can introduce defect at its top and sidewall, the wetability of material improves, the contact area of electrolyte increases, MnO
2can depositional area larger, in addition, the raising of degree of imperfection has activated the chemical property of Graphene, and room, dangling bonds and amorphous carbon etc. more easily catch MnO
2initial forming core, makes deposition process easier, adds Graphene and MnO
2between adhesion.Therefore, combination electrode material, after the surface treatment of Ar gas, can significantly improve the quality that electrochemistry prepares combination electrode.
Embodiment two: present embodiment and embodiment one unlike: the electric conducting material described in step one is metallic nickel, aluminium, iron, gold, nickel foam, carbon cloth or graphite paper.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two unlike: pass into hydrogen in step one, regulate hydrogen gas flow to be 20sccm.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: in step one under pressure is 200Pa and hydrogen atmosphere, by temperature most 700 DEG C in 30min.Other is identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: regulate the gas flow of methane to be 40sccm in step 2, regulate the gas flow of argon gas to be 90sccm.Other is identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: regulate pressure in plasma enhanced chemical vapor deposition vacuum plant to be 400Pa in step 2.Other is identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: in step 2 radio-frequency power be 150W, pressure deposits under be 400Pa and temperature being the condition of 700 DEG C, sedimentation time is 30min.Other is identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: stop in step 3 passing into methane gas, adjustments argon flow amount is 40sccm, and in adjustment plasma enhanced chemical vapor deposition vacuum plant, pressure is 300Pa.Other is identical with embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: in step 3 argon gas atmosphere, pressure be 300Pa, under radio-frequency power be 200W and temperature is the condition of 700 DEG C, etching 5min.Other is identical with embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: in step 5 with etching after graphene substrate material for positive pole, take platinized platinum as negative pole, graphene substrate material positive pole after etching and platinized platinum negative pole are put into electrolyte, then applying constant current at positive pole and negative pole both sides, is 40mA/cm in the current density of constant current
2lower deposition 30min, deposits rear washed with de-ionized water, and to be placed in temperature be that the baking box of 120 DEG C dries 60min, namely completes the preparation method of needle-like manganese dioxide/graphene combination electrode material; The metabisulfite solution of described electrolyte to be concentration be 0.3mol/L and concentration are the mixed solution of the manganese sulfate solution of 0.3mol/L; The volume ratio of described concentration to be the metabisulfite solution of 0.3mol/L and concentration the be manganese sulfate solution of 0.3mol/L is 1:1.Other is identical with embodiment one to nine.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one:
The preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material described in the present embodiment, specifically carries out according to following steps:
One, electric conducting material is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, pass into hydrogen, hydrogen gas flow is regulated to be 20sccm, pressure in plasma enhanced chemical vapor deposition vacuum plant is regulated to be 200Pa, and under pressure is 200Pa and hydrogen atmosphere, by temperature most 700 DEG C in 30min;
Two, argon gas and methane gas is passed into, the gas flow regulating methane is 40sccm, the gas flow regulating argon gas is 90sccm, pressure in plasma enhanced chemical vapor deposition vacuum plant is regulated to be 400Pa, then radio-frequency power be 150W, pressure deposits under be 400Pa and temperature being the condition of 700 DEG C, sedimentation time is 30min;
Three, after deposition terminates, stop passing into methane gas, adjustment argon flow amount is 40sccm, regulates pressure in plasma enhanced chemical vapor deposition vacuum plant to be 300Pa, then argon gas atmosphere, pressure be 300Pa, under radio-frequency power be 200W and temperature is the condition of 700 DEG C, etching 5min;
Four, after etching terminates, be 5 DEG C/s with cooling rate, be 700 DEG C from temperature and be cooled to room temperature, take out, obtain the graphene substrate material after etching;
Five, with the graphene substrate material after etching for positive pole, take platinized platinum as negative pole, graphene substrate material positive pole after etching and platinized platinum negative pole are put into electrolyte, and then applying constant current at positive pole and negative pole both sides, is 40mA/cm in the current density of constant current
2lower deposition 30min, deposits rear washed with de-ionized water, and to be placed in temperature be that the baking box of 120 DEG C dries 60min, namely completes the preparation method of needle-like manganese dioxide/graphene combination electrode material;
The metabisulfite solution of described electrolyte to be concentration be 0.3mol/L and concentration are the mixed solution of the manganese sulfate solution of 0.3mol/L; The volume ratio of described concentration to be the metabisulfite solution of 0.3mol/L and concentration the be manganese sulfate solution of 0.3mol/L is 1:1;
Electric conducting material described in step one is graphite paper.
Fig. 1 is the scanning electron microscope (SEM) photograph of needle-like manganese dioxide/graphene combination electrode material prepared by embodiment one.As seen from the figure, manganese dioxide in fine and close needle-like and perpendicular to VFG substrate grown, and has good dispersiveness and uniformity.
Fig. 2 is the cyclic voltammetry curve of needle-like manganese dioxide/graphene combination electrode material prepared by embodiment one.As seen from the figure, the manganese dioxide of acicular texture has excellent chemical property, its ratio capacitance under 2mV/s sweeps fast condition up to 12000 μ F/cm
2.In cycle life test, this electrode material is 10
4still can keep stable state after secondary circulation, ratio capacitance reaches original 93%, relative to Direct precipitation MnO on orthotropic Graphene
2electrode material improve nearly 20%.
Claims (10)
1. a preparation method for needle-like manganese dioxide/graphene combination electrode material, is characterized in that it carries out according to following steps:
One, electric conducting material is placed in plasma enhanced chemical vapor deposition vacuum plant, being evacuated to pressure is below 5Pa, pass into hydrogen, hydrogen gas flow is regulated to be 10sccm ~ 50sccm, pressure in plasma enhanced chemical vapor deposition vacuum plant is regulated to be 150Pa ~ 350Pa, and under pressure is 150Pa ~ 350Pa and hydrogen atmosphere, by temperature most 500 DEG C ~ 700 DEG C in 20min ~ 60min;
Two, argon gas and methane gas is passed into, the gas flow regulating methane is 35sccm ~ 45sccm, the gas flow regulating argon gas is 80sccm ~ 100sccm, pressure in plasma enhanced chemical vapor deposition vacuum plant is regulated to be 300Pa ~ 500Pa, then radio-frequency power be 100W ~ 200W, pressure deposits under be 300Pa ~ 500Pa and temperature being the condition of 500 DEG C ~ 700 DEG C, sedimentation time is 20min ~ 35min;
Three, after deposition terminates, stop passing into methane gas, adjustment argon flow amount is 20sccm ~ 80sccm, pressure in plasma enhanced chemical vapor deposition vacuum plant is regulated to be 100Pa ~ 400Pa, then argon gas atmosphere, pressure be 100Pa ~ 400Pa, under radio-frequency power be 75W ~ 225W and temperature is the condition of 500 DEG C ~ 700 DEG C, etching 30s ~ 10min;
Four, after etching terminates, with cooling rate be 5 DEG C/s ~ 20 DEG C/s, be 500 DEG C ~ 700 DEG C from temperature and be cooled to room temperature, take out, obtain the graphene substrate material after etching;
Five, with the graphene substrate material after etching for positive pole, take platinized platinum as negative pole, graphene substrate material positive pole after etching and platinized platinum negative pole are put into electrolyte, and then applying constant current at positive pole and negative pole both sides, is 0.5mA/cm in the current density of constant current
2~ 50mA/cm
2lower deposition 1min ~ 60min, deposits rear washed with de-ionized water, and to be placed in temperature be that the baking box of 80 DEG C ~ 120 DEG C dries 30min ~ 120min, namely completes the preparation method of needle-like manganese dioxide/graphene combination electrode material;
The metabisulfite solution of described electrolyte to be concentration be 0.1mol/L ~ 0.3mol/L and concentration are the mixed solution of the manganese sulfate solution of 0.1mol/L ~ 0.3mol/L; The volume ratio of described concentration to be the metabisulfite solution of 0.1mol/L ~ 0.3mol/L and concentration the be manganese sulfate solution of 0.1mol/L ~ 0.3mol/L is 1:1.
2. the preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material according to claim 1, is characterized in that the electric conducting material described in step one is metallic nickel, aluminium, iron, gold, nickel foam, carbon cloth or graphite paper.
3. the preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material according to claim 1, is characterized in that passing into hydrogen in step one, regulates hydrogen gas flow to be 20sccm.
4. the preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material according to claim 1, is characterized in that in step one under pressure is 200Pa and hydrogen atmosphere, by temperature most 700 DEG C in 30min.
5. the preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material according to claim 1, is characterized in that regulating in step 2 the gas flow of methane to be 40sccm, and the gas flow regulating argon gas is 90sccm.
6. the preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material according to claim 1, is characterized in that regulating in step 2 pressure in plasma enhanced chemical vapor deposition vacuum plant to be 400Pa.
7. the preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material according to claim 1, it is characterized in that in step 2 radio-frequency power be 150W, pressure deposits under be 400Pa and temperature being the condition of 700 DEG C, sedimentation time is 30min.
8. the preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material according to claim 1, it is characterized in that stopping in step 3 passing into methane gas, adjustment argon flow amount is 40sccm, regulates pressure in plasma enhanced chemical vapor deposition vacuum plant to be 300Pa.
9. the preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material according to claim 1, it is characterized in that in step 3 argon gas atmosphere, pressure be 300Pa, under radio-frequency power be 200W and temperature is the condition of 700 DEG C, etching 5min.
10. the preparation method of a kind of needle-like manganese dioxide/graphene combination electrode material according to claim 1, it is characterized in that in step 5 with etching after graphene substrate material for positive pole, take platinized platinum as negative pole, graphene substrate material positive pole after etching and platinized platinum negative pole are put into electrolyte, then applying constant current at positive pole and negative pole both sides, is 40mA/cm in the current density of constant current
2lower deposition 30min, deposits rear washed with de-ionized water, and to be placed in temperature be that the baking box of 120 DEG C dries 60min, namely completes the preparation method of needle-like manganese dioxide/graphene combination electrode material; The metabisulfite solution of described electrolyte to be concentration be 0.3mol/L and concentration are the mixed solution of the manganese sulfate solution of 0.3mol/L; The volume ratio of described concentration to be the metabisulfite solution of 0.3mol/L and concentration the be manganese sulfate solution of 0.3mol/L is 1:1.
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| CN106946245A (en) * | 2017-03-20 | 2017-07-14 | 上海大学 | A kind of preparation method of needle-like manganese dioxide/graphene oxide composite nano materials |
| CN106952739A (en) * | 2017-04-06 | 2017-07-14 | 苏州烯电新材料科技有限公司 | A kind of method that Al colelctor electrodes prepare three-dimensional structure electrode material |
| CN109087821A (en) * | 2018-04-10 | 2018-12-25 | 新乡学院 | Hydroxyl manganese oxide self-supporting combination electrode and its preparation method and application |
| CN111009644A (en) * | 2019-11-13 | 2020-04-14 | 天津工业大学 | Preparation method of nano-porous copper surface modified MnO/graphene composite electrode |
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| CN106946245A (en) * | 2017-03-20 | 2017-07-14 | 上海大学 | A kind of preparation method of needle-like manganese dioxide/graphene oxide composite nano materials |
| CN106952739A (en) * | 2017-04-06 | 2017-07-14 | 苏州烯电新材料科技有限公司 | A kind of method that Al colelctor electrodes prepare three-dimensional structure electrode material |
| CN106952739B (en) * | 2017-04-06 | 2018-10-16 | 哈尔滨工大华策科技有限公司 | A kind of method that Al collectors prepare three-dimensional structure electrode material |
| CN109087821A (en) * | 2018-04-10 | 2018-12-25 | 新乡学院 | Hydroxyl manganese oxide self-supporting combination electrode and its preparation method and application |
| CN111009644A (en) * | 2019-11-13 | 2020-04-14 | 天津工业大学 | Preparation method of nano-porous copper surface modified MnO/graphene composite electrode |
| CN111009644B (en) * | 2019-11-13 | 2023-09-22 | 天津工业大学 | Preparation method of nano-porous copper surface modified MnO/graphene composite electrode |
| CN113292142A (en) * | 2021-04-06 | 2021-08-24 | 浙江大学 | Photoelectric synergistic capacitive deionization electrode material and preparation method and application thereof |
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