CN103854876A - Preparation method for self-supporting graphene-manganese oxide composite electrode materials - Google Patents
Preparation method for self-supporting graphene-manganese oxide composite electrode materials Download PDFInfo
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- CN103854876A CN103854876A CN201310727139.1A CN201310727139A CN103854876A CN 103854876 A CN103854876 A CN 103854876A CN 201310727139 A CN201310727139 A CN 201310727139A CN 103854876 A CN103854876 A CN 103854876A
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Abstract
The invention discloses a preparation method for self-supporting graphene-manganese oxide composite electrode materials. The preparation method comprises the steps that flexible graphite paper is placed into an electrolyte, an electrolyzer is a direct-current power supply, two pieces of flexible graphite paper are connected with the positive electrode and the negative electrode of the power supply respectively, the two electrodes are opposite to each other in parallel, the distance between the two electrodes is 1 cm, the voltage is slowly adjusted to range from 1 V to 20 V, the electrolysis time ranges from 0.5 min to 50 min, then the flexible graphite paper at the positive electrode is taken out, the electrolysis portion of the corresponding flexible graphite paper is washed by distilled water, and the washed flexible graphite paper is placed into a vacuum drying box to be dried. According to the preparation method for the self-supporting graphene-manganese oxide composite electrode materials, self-supporting graphene is obtained on the flexible graphite paper, manganese oxide is deposited on the surface of the graphene, and electrolytic deposition is achieved at a time. Compared with the prior art, the preparation process is greatly simplified, efficiency is improved, and the cost is reduced.
Description
Technical field
The present invention relates to a kind of preparation method of electrode material.
Background technology
Along with the arrival of shortage of resources and energy crisis, development of new regenerative resource has become the common problem of paying close attention in the whole world, and the storage of energy and conversion also seem especially important.In current energy storage device, large-scale application of fuel cell, storage battery and traditional capacitor, ultracapacitor is as a kind of Novel energy storage apparatus, the deficiency that has made up the energy density that power density that battery is low and traditional capacitor are low, has a wide range of applications in the field such as Aero-Space, telecommunications.Graphene has large surface area and high conductance, is the selection desirable as electrode material for super capacitor.But Graphene also has the deficiency of easy reunion, this is restricting its development undoubtedly.
Some researchers adopt manganese oxide compound method with it, have so both reduced the reunion of Graphene, and simultaneous oxidation manganese can be contributed again large fake capacitance (CN102468057A, CN103035417A).But its preparation process mostly wastes time and energy, can not settle at one go; Simultaneously the compound material require of powder carries out electro-chemical test being compressed on collector, and this makes again technological process further loaded down with trivial details; Sample preparation process needs to add conductive agent, binding agent sometimes, is difficult to ensure the pure property of effective substance.
Summary of the invention
The object of the present invention is to provide a kind of simple process, with low cost, can effectively avoid Graphene to reunite, the preparation method of self-supporting Graphene-manganese oxide composite electrodes material that electric conductivity is good.The present invention obtains the self-supporting Graphene take flexible graphite paper as substrate by one-step method in-situ electrolysis flexible graphite paper, deposits manganese oxide simultaneously, obtains self-supporting Graphene-manganese oxide composite electrodes material.
Preparation method of the present invention is as follows:
(1) flexible graphite paper is cut into the square of 2 × 2cm, it is neat that the flexible graphite paper edge being cut into is wanted, and the two sides epoxy encapsulation of flexible graphite paper only simultaneously stays the square of 1 × 1cm as electrolysis position therein.
(2) in container, add electrolyte, described electrolyte is that concentration is the Mn (CH of 0.001～0.1mol/L
3cOO)
2, MnSO
4deng the cation soluble-salt solution of manganese, then drip H
2sO
4, the pH value that makes solution is 0.1～6.
(3) electrolysis unit is DC power supply, get two and connect respectively positive source and negative pole through cutting out the flexible graphite paper encapsulating, the square electrolysis position of two flexible graphite papers is dipped in below the liquid level of electrolyte completely, keep electrolysis position parallel just right simultaneously, electrode spacing is 1cm, more than the field intensity between two flexible graphite papers will reach 100V/m; Start when electrolysis, slowly regulation voltage to 1～20V, electrolysis time is 0.5～50min, takes out afterwards the flexible graphite paper of anode, and with distilled water flushing electrolysis position straight to pH value be 7.
(4) flexible graphite paper after rinsing being put into vacuum drying chamber dries.
The present invention compared with prior art tool has the following advantages:
(1) the self-supporting Graphene obtaining is difficult for reuniting, and is combined firmly with substrate, has increased electric capacity and has reduced again resistance;
(2) electrolytic deposition is carried out simultaneously, settle at one go, without adding conductive agent, binding agent, reduced the operating time, simplified technique;
(3) good, the stable in properties, with low cost of the combination electrode material electric conductivity of gained.
Accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope figure of self-supporting Graphene-manganese oxide composite electrodes material of obtaining of the embodiment of the present invention 1.
Fig. 2 is the cyclic voltammetry figure of self-supporting Graphene-manganese oxide composite electrodes material of obtaining of the embodiment of the present invention 1.
Embodiment
Embodiment 1
Flexible graphite paper is cut into the square of 2 × 2cm with sharp scissors, it is neat that the flexible graphite paper edge being cut into is wanted, the two sides epoxy encapsulation of flexible graphite paper, and only one side stays the square of 1 × 1cm as electrolysis position therein.In beaker, add the Mn (CH of 20mL0.05mol/L
3cOO)
2solution, then drip H
2sO
4regulating pH value is 3.Electrolysis unit is DC power supply, get two and connect respectively positive source and negative pole through cutting out the flexible graphite paper encapsulating, the square electrolysis position of two flexible graphite papers is dipped in below the liquid level of electrolyte completely, keeps electrolysis position parallel just right simultaneously, electrode spacing is 1cm.Start when electrolysis, slowly regulation voltage is to 8V, and electrolysis time is 10min, takes out afterwards the flexible graphite paper of anode, and with distilled water flushing electrolysis position straight to pH value be 7.Flexible graphite paper after rinsing is placed on to 30min oven dry at 70 ℃ in vacuum drying chamber.
After in-situ electrolysis, the microscopic appearance of combination electrode material is characterized by ESEM (SEM), and result as shown in Figure 1, can be found out at the Graphene of the condition lower leaf of electrolysis and be deposited on surperficial manganese oxide.
As shown in Figure 2, the combination electrode material of gained is carried out to cyclic voltammetry with three-electrode system, take saturated calomel electrode as reference electrode, platinized platinum is to electrode, and the combination electrode material that the present embodiment obtains is work electrode, the Na of 0.5mol/L
2sO
4solution is made end liquid, and sweep speed is respectively 100,50,20,10,5,2mV/s, is 270mF/cm through calculating the maximum area obtaining than electric capacity
2, the biggest quality is 389F/g than electric capacity.
Flexible graphite paper is cut into the square of 2 × 2cm with sharp scissors, it is neat that the flexible graphite paper edge being cut into is wanted, the two sides epoxy encapsulation of flexible graphite paper, and only one side stays the square of 1 × 1cm as electrolysis position therein.In beaker, add the MnSO of 20mL0.05mol/L
4solution, then drip H
2sO
4regulating pH value is 3.Electrolysis unit is DC power supply, get two and connect respectively positive source and negative pole through cutting out the flexible graphite paper encapsulating, the square electrolysis position of two flexible graphite papers is dipped in below the liquid level of electrolyte completely, keeps electrolysis position parallel just right simultaneously, electrode spacing is 1cm.Start when electrolysis, slowly regulation voltage is to 8V, and electrolysis time is 10min, takes out afterwards the flexible graphite paper of anode, and with distilled water flushing electrolysis position straight to pH value be 7.Flexible graphite paper after rinsing is placed on to 30min oven dry at 80 ℃ in vacuum drying chamber.
Embodiment 3
Flexible graphite paper is cut into the square of 2 × 2cm with sharp scissors, it is neat that the flexible graphite paper edge being cut into is wanted, the two sides epoxy encapsulation of flexible graphite paper, and only one side stays the square of 1 × 1cm as electrolysis position therein.In beaker, add the MnSO of 20mL0.05mol/L
4solution, then drip H
2sO
4regulating pH value is 6.Electrolysis unit is DC power supply, get two and connect respectively positive source and negative pole through cutting out the flexible graphite paper encapsulating, the square electrolysis position of two flexible graphite papers is dipped in below the liquid level of electrolyte completely, keeps electrolysis position parallel just right simultaneously, electrode spacing is 1cm.Start when electrolysis, slowly regulation voltage is to 10V, and electrolysis time is 20min, takes out afterwards the flexible graphite paper of anode, and with distilled water flushing electrolysis position straight to pH value be 7.Flexible graphite paper after rinsing is placed on to 30min oven dry at 70 ℃ in vacuum drying chamber.
Embodiment 4
Flexible graphite paper is cut into the square of 2 × 2cm with sharp scissors, it is neat that the flexible graphite paper edge being cut into is wanted, the two sides epoxy encapsulation of flexible graphite paper, and only one side stays the square of 1 × 1cm as electrolysis position therein.In beaker, add the Mn (CH of 20mL0.001mol/L
3cOO)
2solution, then drip H
2sO
4regulating pH value is 5.Electrolysis unit is DC power supply, get two and connect respectively positive source and negative pole through cutting out the flexible graphite paper encapsulating, the square electrolysis position of two flexible graphite papers is dipped in below the liquid level of electrolyte completely, keeps electrolysis position parallel just right simultaneously, electrode spacing is 1cm.Start when electrolysis, slowly regulation voltage is to 20V, and electrolysis time is 30min, takes out afterwards the flexible graphite paper of anode, and with distilled water flushing electrolysis position straight to pH value be 7.Flexible graphite paper after rinsing is placed on to 30min oven dry at 70 ℃ in vacuum drying chamber.
Flexible graphite paper is cut into the square of 2 × 2cm with sharp scissors, it is neat that the flexible graphite paper edge being cut into is wanted, the two sides epoxy encapsulation of flexible graphite paper, and only one side stays the square of 1 × 1cm as electrolysis position therein.In beaker, add the Mn (CH of 20mL0.1mol/L
3cOO)
2solution, then drip H
2sO
4regulating pH value is 6.Electrolysis unit is DC power supply, get two and connect respectively positive source and negative pole through cutting out the flexible graphite paper encapsulating, the square electrolysis position of two flexible graphite papers is dipped in below the liquid level of electrolyte completely, keeps electrolysis position parallel just right simultaneously, electrode spacing is 1cm.Start when electrolysis, slowly regulation voltage is to 8V, and electrolysis time is 40min, takes out afterwards the flexible graphite paper of anode, and with distilled water flushing electrolysis position straight to pH value be 7.Flexible graphite paper after rinsing is placed on to 30min oven dry at 80 ℃ in vacuum drying chamber.
Embodiment 6
Flexible graphite paper is cut into the square of 2 × 2cm with sharp scissors, it is neat that the flexible graphite paper edge being cut into is wanted, the two sides epoxy encapsulation of flexible graphite paper, and only one side stays the square of 1 × 1cm as electrolysis position therein.In beaker, add the Mn (CH of 20mL0.1mol/L
3cOO)
2solution, then drip H
2sO
4regulating pH value is 0.1.Electrolysis unit is DC power supply, get two and connect respectively positive source and negative pole through cutting out the flexible graphite paper encapsulating, the square electrolysis position of two flexible graphite papers is dipped in below the liquid level of electrolyte completely, keeps electrolysis position parallel just right simultaneously, electrode spacing is 1cm.Start when electrolysis, slowly regulation voltage is to 1V, and electrolysis time is 50min, takes out afterwards the flexible graphite paper of anode, and with distilled water flushing electrolysis position straight to pH value be 7.Flexible graphite paper after rinsing is placed on to 30min oven dry at 80 ℃ in vacuum drying chamber.
Embodiment 7
Flexible graphite paper is cut into the square of 2 × 2cm with sharp scissors, it is neat that the flexible graphite paper edge being cut into is wanted, the two sides epoxy encapsulation of flexible graphite paper, and only one side stays the square of 1 × 1cm as electrolysis position therein.In beaker, add the Mn (CH of 20mL0.06mol/L
3cOO)
2solution, then drip H
2sO
4regulating pH value is 0.1.Electrolysis unit is DC power supply, get two and connect respectively positive source and negative pole through cutting out the flexible graphite paper encapsulating, the square electrolysis position of two flexible graphite papers is dipped in below the liquid level of electrolyte completely, keeps electrolysis position parallel just right simultaneously, electrode spacing is 1cm.Start when electrolysis, slowly regulation voltage is to 20V, and electrolysis time is 0.5min, takes out afterwards the flexible graphite paper of anode, and with distilled water flushing electrolysis position straight to pH value be 7.Flexible graphite paper after rinsing is placed on to 30min oven dry at 80 ℃ in vacuum drying chamber.
Claims (1)
1. a preparation method for self-supporting Graphene-manganese oxide composite electrodes material, is characterized in that:
(1) flexible graphite paper is cut into the square of 2 × 2cm, it is neat that the flexible graphite paper edge being cut into is wanted, the two sides epoxy encapsulation of flexible graphite paper, and only one side stays the square of 1 × 1cm as electrolysis position therein.
(2) in container, add electrolyte, described electrolyte is that concentration is the Mn (CH of 0.001～0.1mol/L
3cOO)
2, MnSO
4deng the cation soluble-salt solution of manganese, then drip H
2sO
4the pH value of regulator solution is 0.1～6.
(3) electrolysis unit is DC power supply, get two and connect respectively positive source and negative pole through cutting out the flexible graphite paper encapsulating, the square electrolysis position of two flexible graphite papers is dipped in below the liquid level of electrolyte completely, keep electrolysis position parallel just right simultaneously, electrode spacing is 1cm, more than the field intensity between two flexible graphite papers will reach 100V/m; Start when electrolysis, slowly regulation voltage to 1～20V, electrolysis time is 0.5～50min, takes out afterwards the flexible graphite paper of anode, and with distilled water flushing electrolysis position straight to pH value be 7.
(4) flexible graphite paper after rinsing being put into vacuum drying chamber dries.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104900864A (en) * | 2015-04-10 | 2015-09-09 | 武汉大学 | Manganese dioxide/graphene lithium ion battery cathode material and preparation method thereof |
| CN107754786A (en) * | 2017-10-16 | 2018-03-06 | 广西大学 | One kind utilizes KMnO4The method that electrocatalytic oxidation is improved on direct oxidation graphite paper |
| CN108273495A (en) * | 2017-12-20 | 2018-07-13 | 广西大学 | A kind of preparation method of multi-pore channel graphite paper |
| CN109360745A (en) * | 2018-11-26 | 2019-02-19 | 阜阳师范学院 | A kind of preparation method of graphene combination electrode |
| CN112447945A (en) * | 2019-09-04 | 2021-03-05 | 盐城市新能源化学储能与动力电源研究中心 | 3D graphene carbon-nickel-metal hydride battery and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104900864A (en) * | 2015-04-10 | 2015-09-09 | 武汉大学 | Manganese dioxide/graphene lithium ion battery cathode material and preparation method thereof |
| CN107754786A (en) * | 2017-10-16 | 2018-03-06 | 广西大学 | One kind utilizes KMnO4The method that electrocatalytic oxidation is improved on direct oxidation graphite paper |
| CN107754786B (en) * | 2017-10-16 | 2020-06-16 | 广西大学 | By using KMnO4Method for improving electrocatalytic oxidation on direct oxidized graphite paper |
| CN108273495A (en) * | 2017-12-20 | 2018-07-13 | 广西大学 | A kind of preparation method of multi-pore channel graphite paper |
| CN108273495B (en) * | 2017-12-20 | 2020-08-18 | 广西大学 | Preparation method of multi-pore-passage graphite paper |
| CN109360745A (en) * | 2018-11-26 | 2019-02-19 | 阜阳师范学院 | A kind of preparation method of graphene combination electrode |
| CN112447945A (en) * | 2019-09-04 | 2021-03-05 | 盐城市新能源化学储能与动力电源研究中心 | 3D graphene carbon-nickel-metal hydride battery and preparation method thereof |
| CN112447945B (en) * | 2019-09-04 | 2022-06-28 | 盐城师范学院 | 3D graphene based carbon-nickel hydride battery and preparation method thereof |
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