CN103854875A - Polyaniline/MnO2 compound modified three-dimensional graphene composite material, preparation method and application of composite material - Google Patents
Polyaniline/MnO2 compound modified three-dimensional graphene composite material, preparation method and application of composite material Download PDFInfo
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Abstract
The invention discloses a polyaniline/MnO2 compound modified three-dimensional graphene composite material, a preparation method and application of the composite material. The preparation method comprises the following steps: dissolving manganese salt and an aniline monomer into dilute sulphuric acid solution with the concentration being 0.1-0.5mol/L, adding three-dimensional graphene serving as a working electrode, a saturated calomel electrode serving as a reference electrode and a platinum electrode serving as a counter electrode into the solution, performing electrochemical deposition by utilizing cyclic voltammetry, forming a compound from the polyaniline and MnO2 and depositing the compound in the three-dimensional graphene so as to obtain the polyaniline/MnO2 compound modified three-dimensional graphene composite material. The invention has the obvious characteristics that (1) raw materials are cheap, the compounding process is simple and convenient, the preparation cost is low and large-scale production is facilitated; (2) the ratio of the components of the component material can be controlled by controlling the scanning parameters of cyclic voltammetry and the amount of reactants; (3) the composite material has high specific electric capacity and stable electrochemical performance.
Description
Technical field
The present invention relates to a kind of polyaniline/MnO
2compound is modified three-dimensional graphene composite material and its preparation method and application, belongs to composite material, electrode material for super capacitor preparation field.
Background technology
Ultracapacitor is that electrochemical capacitor is a kind of novel energy-storing device between traditional capacitor and secondary cell.Compared with traditional capacitor, electrochemical capacitor has higher specific capacity, and the 10-100 that storable specific energy is traditional capacitor doubly; Compared with battery, there is the advantages such as specific power is high, energy density is large, the charging interval is short, discharging efficiency is high and have extended cycle life.There is of crucial importance and wide application prospect in fields such as mechanics of communication, electric automobile and Aero-Space science and techniques of defence.
The capacitive property of ultracapacitor depends primarily on electrode material, mainly contains three classes, various material with carbon elements at present for the material of electric chemical super capacitor; Oxide and the hydroxide etc. of ruthenic oxide, manganese dioxide and nickel; Conducting polymer materials etc.But the material with carbon element of one-component is not high as the ratio electric capacity of ultracapacitor, the metal oxide of one-component is lower as the conductance of ultracapacitor, electrochemistry cyclicity is undesirable, and the conducting polymer of one-component is low as the energy density of ultracapacitor, cyclical stability is poor.In order to make up above defect, be badly in need of research and development binary or trielement composite material to improve the performance of ultracapacitor.
In recent years, the grapheme material that has unique physical and a chemical property has caused the extensive concern of scientists.Wherein three-dimensional grapheme has abundant pore property, and specific area and porosity are high, and density is low, for basis material provide can be composite filled space, there is potential using value in fields such as electrochemical capacitance, secondary cell and new catalytics.
Summary of the invention
The object of the present invention is to provide a kind of polyaniline/MnO
2compound is modified three-dimensional graphene composite material and its preparation method and application, polyaniline/MnO provided by the invention
2compound modification three-dimensional graphene composite material needed raw material is cheap, and preparation method is simple, higher than electric capacity, and good conductivity has broad application prospects in ultracapacitor field.
The present invention solves the problems of the technologies described above adopted technical scheme: polyaniline/MnO
2compound is modified three-dimensional graphene composite material, and it is following preparation method's products therefrom, comprises the following steps:
Manganese salt, aniline monomer are dissolved in the dilution heat of sulfuric acid that concentration is 0.1-0.5mol/L, using three-dimensional grapheme as work electrode, saturated calomel electrode is as reference electrode, platinum electrode as electrode being placed in to above-mentioned solution, utilize cyclic voltammetry to carry out electrochemical deposition, polyaniline and MnO
2form compound and be deposited in three-dimensional grapheme, obtaining polyaniline/MnO
2compound is modified three-dimensional graphene composite material.
Press such scheme, the scanning potential region that carries out the cyclic voltammetry of electrochemical deposition is-0.2-1.2V, and sweep speed is 20-100mV/s, and the scanning number of turns is 10-20 circle.
Press such scheme, described manganese salt is MnSO
4or Mn (CH
3cOO)
2, concentration is 0.1-0.3mol/L.
Press such scheme, described concentration of aniline is 0.05-0.2mol/L.
Described polyaniline/MnO
2compound is modified the preparation method of three-dimensional graphene composite material, it is characterized in that comprising the following steps:
Manganese salt, aniline monomer are dissolved in the dilution heat of sulfuric acid that concentration is 0.1-0.5mol/L, using three-dimensional grapheme as work electrode, saturated calomel electrode is as reference electrode, platinum electrode as electrode being placed in to above-mentioned solution, utilize cyclic voltammetry to carry out electrochemical deposition, polyaniline and MnO
2form compound and be deposited in three-dimensional grapheme, obtaining polyaniline/MnO
2compound is modified three-dimensional graphene composite material.
Described polyaniline/MnO
2compound is modified the application of three-dimensional graphene composite material as super capacitor material.
The present invention has following distinguishing feature: 1) raw material of composite material is cheap, and combination process is easy, and preparation cost is low, is applicable to large-scale production; 2) sweep parameter by controlled circulation voltammetry and reactant consumption can be controlled the proportioning of composite material component; 3) composite material is by Graphene, MnO
2be combined with each other with electrically conductive polyaniline, the synergy that makes full use of three obtains having the trielement composite material of high-specific capacitance super and stable electrical chemical property.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
1) by the MnSO of 0.1mol/L
4, 0.1mol/L aniline monomer be dissolved in the dilution heat of sulfuric acid that concentration is 0.2mol/L, using three-dimensional grapheme as work electrode, saturated calomel electrode is as reference electrode, platinum electrode as electrode being placed in to above-mentioned solution, utilize cyclic voltammetry to carry out electrochemical deposition, scanning potential region is-0.2-1.2V, sweep speed is 50mV/s, scanning 20 circles, polyaniline and MnO
2form compound and be deposited in three-dimensional grapheme, obtaining polyaniline/MnO
2compound is modified three-dimensional graphene composite material.
2) above-mentioned composite material is carried out to constant current charge-discharge experiment, under 1A/g current density, measuring it is 263F/g than electric capacity, and after 1000 circulations, it is 91.4% than electric capacity conservation rate.
Embodiment 2:
1) by the MnSO of 0.2mol/L
4, 0.2mol/L aniline monomer be dissolved in the dilution heat of sulfuric acid that concentration is 0.2mol/L, using three-dimensional grapheme as work electrode, saturated calomel electrode is as reference electrode, platinum electrode as electrode being placed in to above-mentioned solution, utilize cyclic voltammetry to carry out electrochemical deposition, scanning potential region is-0.2-1.2V, sweep speed is 20mV/s, scanning 10 circles, polyaniline and MnO
2form compound and be deposited in three-dimensional grapheme, obtaining polyaniline/MnO
2compound is modified three-dimensional graphene composite material.
2) above-mentioned composite material is carried out to constant current charge-discharge experiment, under 1A/g current density, measuring it is 286F/g than electric capacity, and after 1000 circulations, it is 92.1% than electric capacity conservation rate.
Embodiment 3:
1) by the Mn (CH of 0.1mol/L
3cOO)
2, 0.05mol/L aniline monomer be dissolved in the dilution heat of sulfuric acid that concentration is 0.1mol/L, using three-dimensional grapheme as work electrode, saturated calomel electrode is as reference electrode, platinum electrode as electrode being placed in to above-mentioned solution, utilize cyclic voltammetry to carry out electrochemical deposition, scanning potential region is-0.2-1.2V, sweep speed is 50mV/s, scanning 15 circles, polyaniline and MnO
2form compound and be deposited in three-dimensional grapheme, obtaining polyaniline/MnO
2compound is modified three-dimensional graphene composite material.
2) above-mentioned composite material is carried out to constant current charge-discharge experiment, under 1A/g current density, measuring it is 224F/g than electric capacity, and after 1000 circulations, it is 90.8% than electric capacity conservation rate.
Embodiment 4:
1) by the Mn (CH of 0.15mol/L
3cOO)
2, 0.15mol/L aniline monomer be dissolved in the dilution heat of sulfuric acid that concentration is 0.3mol/L, using three-dimensional grapheme as work electrode, saturated calomel electrode is as reference electrode, platinum electrode as electrode being placed in to above-mentioned solution, utilize cyclic voltammetry to carry out electrochemical deposition, scanning potential region is-0.2-1.2V, sweep speed is 100mV/s, scanning 15 circles, polyaniline and MnO
2form compound and be deposited in three-dimensional grapheme, obtaining polyaniline/MnO
2compound is modified three-dimensional graphene composite material.
2) above-mentioned composite material is carried out to constant current charge-discharge experiment, under 1A/g current density, measuring it is 272F/g than electric capacity, and after 1000 circulations, it is 91.5% than electric capacity conservation rate.
Embodiment 5:
1) by the Mn (CH of 0.3mol/L
3cOO)
2, 0.2mol/L aniline monomer be dissolved in the dilution heat of sulfuric acid that concentration is 0.2mol/L, using three-dimensional grapheme as work electrode, saturated calomel electrode is as reference electrode, platinum electrode as electrode being placed in to above-mentioned solution, utilize cyclic voltammetry to carry out electrochemical deposition, scanning potential region is-0.2-1.2V, sweep speed is 50mV/s, scanning 20 circles, polyaniline and MnO
2form compound and be deposited in three-dimensional grapheme, obtaining polyaniline/MnO
2compound is modified three-dimensional graphene composite material.
2) above-mentioned composite material is carried out to constant current charge-discharge experiment, under 1A/g current density, measuring it is 293F/g than electric capacity, and after 1000 circulations, it is 90.1% than electric capacity conservation rate.
Embodiment 6:
1) by the Mn (CH of 0.2mol/L
3cOO)
2, 0.15mol/L aniline monomer be dissolved in the dilution heat of sulfuric acid that concentration is 0.4mol/L, using three-dimensional grapheme as work electrode, saturated calomel electrode is as reference electrode, platinum electrode as electrode being placed in to above-mentioned solution, utilize cyclic voltammetry to carry out electrochemical deposition, scanning potential region is-0.2-1.2V, sweep speed is 50mV/s, scanning 20 circles, polyaniline and MnO
2form compound and be deposited in three-dimensional grapheme, obtaining polyaniline/MnO
2compound is modified three-dimensional graphene composite material.
2) above-mentioned composite material is carried out to constant current charge-discharge experiment, under 1A/g current density, measuring it is 268F/g than electric capacity, and after 1000 circulations, it is 91.6% than electric capacity conservation rate.
Embodiment 7:
1) by the MnSO of 0.1mol/L
4, 0.2mol/L aniline monomer be dissolved in the dilution heat of sulfuric acid that concentration is 0.5mol/L, using three-dimensional grapheme as work electrode, saturated calomel electrode is as reference electrode, platinum electrode as electrode being placed in to above-mentioned solution, utilize cyclic voltammetry to carry out electrochemical deposition, scanning potential region is-0.2-1.2V, sweep speed is 20mV/s, scanning 10 circles, polyaniline and MnO
2form compound and be deposited in three-dimensional grapheme, obtaining polyaniline/MnO
2compound is modified three-dimensional graphene composite material.
2) above-mentioned composite material is carried out to constant current charge-discharge experiment, under 1A/g current density, measuring it is 242F/g than electric capacity, and after 1000 circulations, it is 92.3% than electric capacity conservation rate.
The cited each raw material of the present invention can be realized the present invention, and the bound value of each raw material, interval value can realize the present invention; Do not enumerate embodiment at this.Bound value, the interval value of technological parameter of the present invention can be realized the present invention, do not enumerate embodiment at this.
Claims (9)
1. polyaniline/MnO
2compound is modified three-dimensional graphene composite material, and it is following preparation method's products therefrom, comprises the following steps:
Manganese salt, aniline monomer are dissolved in the dilution heat of sulfuric acid that concentration is 0.1-0.5mol/L, using three-dimensional grapheme as work electrode, saturated calomel electrode is as reference electrode, platinum electrode as electrode being placed in to above-mentioned solution, utilize cyclic voltammetry to carry out electrochemical deposition, polyaniline and MnO
2form compound and be deposited in three-dimensional grapheme, obtaining polyaniline/MnO
2compound is modified three-dimensional graphene composite material.
2. polyaniline/MnO according to claim 1
2compound is modified three-dimensional graphene composite material, it is characterized in that: the scanning potential region that carries out the cyclic voltammetry of electrochemical deposition is-0.2-1.2V, and sweep speed is 20-100mV/s, and the scanning number of turns is 10-20 circle.
3. polyaniline/MnO according to claim 1
2compound is modified three-dimensional graphene composite material, it is characterized in that: described manganese salt is MnSO
4or Mn (CH
3cOO)
2, concentration is 0.1-0.3mol/L.
4. polyaniline/MnO according to claim 1
2compound is modified three-dimensional graphene composite material, it is characterized in that: described concentration of aniline is 0.05-0.2mol/L.
5. polyaniline/MnO described in claim 1
2compound is modified the preparation method of three-dimensional graphene composite material, it is characterized in that comprising the following steps:
Manganese salt, aniline monomer are dissolved in the dilution heat of sulfuric acid that concentration is 0.1-0.5mol/L, using three-dimensional grapheme as work electrode, saturated calomel electrode is as reference electrode, platinum electrode as electrode being placed in to above-mentioned solution, utilize cyclic voltammetry to carry out electrochemical deposition, polyaniline and MnO
2form compound and be deposited in three-dimensional grapheme, obtaining polyaniline/MnO
2compound is modified three-dimensional graphene composite material.
6. polyaniline/MnO according to claim 5
2compound is modified the preparation method of three-dimensional graphene composite material, it is characterized in that: the scanning potential region that carries out the cyclic voltammetry of electrochemical deposition is-0.2-1.2V, and sweep speed is 20-100mV/s, and the scanning number of turns is 10-20 circle.
7. polyaniline/MnO according to claim 5
2compound is modified the preparation method of three-dimensional graphene composite material, it is characterized in that: described manganese salt is MnSO
4, Mn (CH
3cOO)
2, concentration is 0.1-0.3mol/L.
8. polyaniline/MnO according to claim 5
2compound is modified the preparation method of three-dimensional graphene composite material, it is characterized in that: described concentration of aniline is 0.05-0.2mol/L.
9. polyaniline/MnO claimed in claim 1
2compound is modified the application of three-dimensional graphene composite material as super capacitor material.
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Cited By (8)
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| CN104332328A (en) * | 2014-10-24 | 2015-02-04 | 东华大学 | Nickel foam base type preparation method of nickel oxide/ polyaniline supercapacitor electrode material |
| CN104559176A (en) * | 2015-01-27 | 2015-04-29 | 西南科技大学 | Preparation method of three-dimensional reduced graphene oxide/polyaniline composite material |
| CN105118681A (en) * | 2015-08-17 | 2015-12-02 | 电子科技大学 | A method for manufacturing a graphene -based ternary composite flexible electrode |
| CN106298286A (en) * | 2016-10-15 | 2017-01-04 | 成都育芽科技有限公司 | The preparation method of Graphene/manganese dioxide/polyaniline nano-rod array and application |
| CN106449148A (en) * | 2016-11-22 | 2017-02-22 | 中国地质大学（北京） | Method for preparing tubular manganese dioxide / poly-aniline / graphene composite material |
| CN107316752A (en) * | 2017-06-14 | 2017-11-03 | 天津理工大学 | A kind of preparation method of the grapheme modified paper capacitor electrode of manganese bioxide/carbon nano tube |
| CN108172412A (en) * | 2017-12-24 | 2018-06-15 | 桂林理工大学 | The preparation method of polypyrrole/nickel hydroxide composite electrode material for super capacitor |
| CN111416096A (en) * | 2020-03-24 | 2020-07-14 | 中南大学 | Graphene oxide/polyaniline/manganese dioxide composite electrode, preparation method thereof and application thereof in seawater battery |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104332328A (en) * | 2014-10-24 | 2015-02-04 | 东华大学 | Nickel foam base type preparation method of nickel oxide/ polyaniline supercapacitor electrode material |
| CN104332328B (en) * | 2014-10-24 | 2017-08-01 | 东华大学 | A kind of preparation method of nickel oxide/polyaniline electrode material for super capacitor using nickel foam as substrate |
| CN104559176A (en) * | 2015-01-27 | 2015-04-29 | 西南科技大学 | Preparation method of three-dimensional reduced graphene oxide/polyaniline composite material |
| CN105118681A (en) * | 2015-08-17 | 2015-12-02 | 电子科技大学 | A method for manufacturing a graphene -based ternary composite flexible electrode |
| CN106298286A (en) * | 2016-10-15 | 2017-01-04 | 成都育芽科技有限公司 | The preparation method of Graphene/manganese dioxide/polyaniline nano-rod array and application |
| CN106449148A (en) * | 2016-11-22 | 2017-02-22 | 中国地质大学（北京） | Method for preparing tubular manganese dioxide / poly-aniline / graphene composite material |
| CN106449148B (en) * | 2016-11-22 | 2018-01-30 | 中国地质大学（北京） | A kind of preparation method of tubulose manganese dioxide/polyaniline/graphene composite material |
| CN107316752A (en) * | 2017-06-14 | 2017-11-03 | 天津理工大学 | A kind of preparation method of the grapheme modified paper capacitor electrode of manganese bioxide/carbon nano tube |
| CN108172412A (en) * | 2017-12-24 | 2018-06-15 | 桂林理工大学 | The preparation method of polypyrrole/nickel hydroxide composite electrode material for super capacitor |
| CN111416096A (en) * | 2020-03-24 | 2020-07-14 | 中南大学 | Graphene oxide/polyaniline/manganese dioxide composite electrode, preparation method thereof and application thereof in seawater battery |
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Application publication date: 20140611 |