CN103594254B - The preparation method of a kind of manganese dioxide/mesoporous carbon nanometer classification combination electrode material - Google Patents

The preparation method of a kind of manganese dioxide/mesoporous carbon nanometer classification combination electrode material Download PDF

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CN103594254B
CN103594254B CN201310608257.0A CN201310608257A CN103594254B CN 103594254 B CN103594254 B CN 103594254B CN 201310608257 A CN201310608257 A CN 201310608257A CN 103594254 B CN103594254 B CN 103594254B
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manganese dioxide
mesoporous carbon
combination electrode
carbon nanometer
carbon
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CN201310608257.0A
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CN103594254A (en
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程起林
姜立学
李春忠
赵洁
杜双双
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华东理工大学
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Abstract

The present invention discloses the preparation method of a kind of manganese dioxide/mesoporous carbon nanometer classification combination electrode material, the method first with manganese sulfate and ammonium persulfate for reactant, be there is by hydro thermal method preparation the sea urchin shape manganese dioxide of certain hollow-core construction, then respectively with the presoma that phenolic resins and tetraethoxysilane are carbon and silicon dioxide, F127 is constitution controller, through volatilization self assembly and carbonization, ordered mesopore carbon and manganese dioxide are combined, finally with the silica nanosphere in sodium hydrate aqueous solution removing material, namely manganese dioxide/mesoporous carbon the nano composite material of hierarchy is obtained.When this material is used as electrode material for super capacitor, its specific capacity exceeds nearly one times than pure manganese dioxide, test result shows that this composite material has played the advantage of material with carbon element high conductivity and manganese dioxide height ratio capacity, improve high rate performance and the cyclical stability of material, show excellent chemical property.

Description

The preparation method of a kind of manganese dioxide/mesoporous carbon nanometer classification combination electrode material

Technical field

The present invention belongs to new energy materials field, relates to a kind of preparation method of electrode material for super capacitor, is specifically related to the preparation of a kind of manganese dioxide/mesoporous carbon nanometer hierarchical composite material.

Technical background

Ultracapacitor is also electrochemical capacitor, is a kind of novel green energy-storage travelling wave tube, because it has the power density higher than battery and and the energy density higher than traditional double electric layer capacitor and obtain extensive concern.Especially the minimizing day by day of fossil fuel reserves along with global energy requirements sustainable growth in recent years, and the environmental pollution that brings of combustion of fossil fuel seriously affects the living environment of the mankind, therefore research and development that are clean, regenerative resource are just seemed very important.Ultracapacitor have simultaneously charge/discharge rates fast, have extended cycle life, the feature such as serviceability temperature wide ranges, environmental pollution are little, this makes it can be applicable to the fields such as hybrid vehicle, portable type electronic product, storage and backup system, integrated mill's facility and military equipment as energy storage device.But existing ultracapacitor still has a lot of shortcoming, such as relatively low energy density, high cost, high self-discharge rate, shortage commercialization standard etc.Electrode material is ultracapacitor core component, and the electrode material of design and development excellence puies forward high performance key.

Ordered mesopore carbon is a kind of novel how empty material with carbon element, and have unique process based prediction model, its ordered mesopore structure is conducive to the fast transport of ion, is widely used as electrode material.Compared with commercialization active carbon material, the ordered mesopore carbon of mesoporous greatly and two-dimentional pore structure shows excellent capacitance behavior, power stage and high rate capability.But relative to metal oxide and this two classes electrode material of conducting polymer, the specific capacity of material with carbon element is low.Manganese dioxide has the advantages such as low, nontoxic, the high theoretical specific capacity of cost, good stability, be desirable electrode material, but resistance is large.Ordered mesopore carbon is permeated and coated major diameter sea urchin shape manganese dioxide, makes both combine, give full play to the cooperative effect between two kinds of different materials, improve specific area and the conductivity of composite material, thus optimize the chemical property of electrode material.

Summary of the invention

In view of above problem, the object of the invention is the preparation method proposing a kind of manganese dioxide/mesoporous carbon nanometer classification combination electrode material, and study its chemical property as electrode material for super capacitor.

Design of the present invention is such: prepare hollow sea urchin shape manganese dioxide by hydro thermal method, it is fully mixed with the presoma phenolic resins of ordered mesopore carbon and the presoma tetraethoxysilane of silicon dioxide, phenolic resins is made to be coated on manganese dioxide surface and to be impregnated into inside, to volatilize under normal temperature self assembly make phenolic resin curing, carbonization in high temperature process furnances subsequently.Manganese dioxide/mesoporous carbon the nano composite material of hierarchy is finally obtained with sodium hydrate aqueous solution removing silica spheres.By the compound of meso-porous carbon material and sea urchin shape manganese dioxide, be conducive to the specific area and the conductivity that improve material, play cooperative effect between the two, improve the chemical property of material.

The present invention is achieved by the following technical solutions:

A preparation method for manganese dioxide/mesoporous carbon nanometer classification combination electrode material, comprises the steps:

(1) 0.5 ~ 1.0g Manganous sulfate monohydrate and 0.6 ~ 1.5g ammonium persulfate are successively joined in 45mL deionized water, stir 40 ~ 80min, pour reactor into and reactor is put into baking oven, 8 ~ 12h is kept in the baking oven of 80 ~ 120 DEG C, the black precipitate deionized water be obtained by reacting and absolute ethanol washing are dried, obtains the sea urchin shape manganese dioxide with hollow-core construction;

(2) hydrochloric acid solution of 0.06 ~ 0.5g0.2M and 0.05 ~ 0.5gPluronicF127 are dissolved in 3 ~ 8g absolute ethyl alcohol, add the phenolic resins ethanolic solution of 0.1 ~ 1.0g tetraethoxysilane and 0.3 ~ 2.5g mass fraction 20% after stirring respectively, continue stirring 15 ~ 30min and obtain mixed solution;

Described mass fraction is that in the phenolic resins ethanolic solution of 20%, ethanol is solvent;

(3) sea urchin shape manganese dioxide 0.1g step (1) obtained joins in the mixed solution of step (2), stirs ultrasonic 2 ~ 4h, is then left standstill volatilization self assembly 3 ~ 6h, and the baking oven insulation 16 ~ 30h putting into 80 ~ 120 DEG C obtains compound;

(4) compound that step (3) obtains is put into high temperature process furnances, 800 ~ 1000 DEG C of insulation 1 ~ 4h, by the phenolic resin carbonized in compound, obtain black product under nitrogen protection;

(5) black product grinding step (4) obtained, the sodium hydrate aqueous solution putting into concentration 1 ~ 2M stirs 16 ~ 30h, and removing silica spheres wherein, is washed till neutrality with a large amount of deionized water and absolute ethyl alcohol, dry, obtain manganese dioxide/mesoporous carbon nanometer classification combination electrode material.

In described manganese dioxide/mesoporous carbon nanometer classification combination electrode material, the diameter of manganese dioxide is 1 ~ 5 μm, surperficial acupuncture length is 500nm ~ 1 μm.

Manganese dioxide/mesoporous carbon the nano composite material of described hierarchy is ordered mesopore carbon infiltration and the structure of coated sea urchin shape manganese dioxide, and different with the change composite surface pattern of carbon content.

Described manganese dioxide/mesoporous carbon nanometer classification combination electrode material is applied in ultracapacitor, and its specific capacity exceeds 0.8 ~ 1 times than pure manganese dioxide, has excellent chemical property.

Beneficial effect of the present invention:

From above technical scheme and implementation method, the present invention with the hollow sea urchin shape manganese dioxide prepared for carrier, make phenolic resins coated and penetrate into its inside, after solidifying also carbonization, the silica spheres removed in material obtains the manganese dioxide/mesoporous carbon nano composite material of hierarchy.The compound of meso-porous carbon material and manganese dioxide, considerably increases specific area and the pore capacities of material, improves the electric double layer capacitance of material.Ordered mesopore carbon is coated on manganese dioxide surface and is applied in its internal structure, be conducive to electrolyte ion transmission in the material and diffusion, reduce the transmission path of electrolyte ion in charge and discharge process, drastically increase the electrochemical utilization rate of manganese dioxide, therefore improve the chemical property of composite material.By the content regulating the consumption of phenolic resins and tetraethoxysilane to control composite material intermediary hole carbon, thus structure and the chemical property of composite material can be affected.Preparation method's process of the present invention is simple, and cheaper starting materials is easy to get, and is easy to large-scale production.Show height ratio capacity with the electrode material that manganese dioxide/mesoporous carbon nanometer hierarchical composite material is obtained, the chemical property that high rate capability and good circulation stability etc. are excellent, can be used for ultracapacitor.

Accompanying drawing explanation

Fig. 1 is the stereoscan photograph of embodiment 1 product;

Fig. 2 is the stereoscan photograph of embodiment 2 product;

Fig. 3 is specific area and the pore-size distribution of manganese dioxide/mesoporous carbon nano composite material prepared by embodiment 1;

Fig. 4 is that the manganese dioxide/mesoporous carbon hierarchical composite material of embodiment 1,2 preparation is at 1Ag -1constant current charge-discharge curve under current density;

Fig. 5 is the cyclic voltammetry curve of manganese dioxide/mesoporous carbon nano composite material prepared by embodiment 1;

Fig. 6 is the stable circulation linearity curve of manganese dioxide/mesoporous carbon nano composite material prepared by embodiment 1.

Embodiment

Be below embodiments of the invention, give detailed execution mode and concrete operating process, its object is only understanding content of the present invention better.Therefore protection scope of the present invention is not by the restriction of illustrated embodiment.

Embodiment 1

0.6761g Manganous sulfate monohydrate and 0.9128g ammonium persulfate are successively joined in 45mL deionized water, stir 60min, pour reactor into and reactor is put into baking oven, 10h is kept at baking oven at 100 DEG C, the black precipitate deionized water be obtained by reacting and absolute ethanol washing are dried, obtains the sea urchin shape manganese dioxide with hollow-core construction.

The hydrochloric acid solution of 0.0625g0.2M and 0.1000gF127 are dissolved in 4g absolute ethyl alcohol, after stirring, add the phenolic resins ethanolic solution of 0.1300g tetraethoxysilane and 0.3125g mass fraction 20% respectively, continue to stir 20min, obtain mixed solution.

Add in above-mentioned mixed solution by the sea urchin shape manganese dioxide 0.1000g of above-mentioned preparation, ultrasonic and stir 3h, at room temperature left standstill volatilization self assembly 5h, put into 100 DEG C, baking oven, insulation 24h, obtains compound.The compound obtained is put into high temperature process furnances, and 900 DEG C of insulation 2h, obtain black product under nitrogen protection.By the black product pulverize obtained, the sodium hydrate aqueous solution putting into concentration 2M stirs 24h, removing silica spheres wherein, neutrality is washed till again with deionized water and absolute ethyl alcohol, manganese dioxide/mesoporous carbon nanometer classification combination electrode material is obtained after oven dry, Fig. 1 is its electromicroscopic photograph, and its specific area and pore-size distribution are as shown in Figure 3.

Embodiment 2

0.6761g Manganous sulfate monohydrate and 0.9128g ammonium persulfate are successively joined in 45mL deionized water, stir 60min, pour reactor into and reactor is put into baking oven, 10h is kept at baking oven at 100 DEG C, the black precipitate deionized water be obtained by reacting and absolute ethanol washing are dried, obtains the sea urchin shape manganese dioxide with hollow-core construction.

The hydrochloric acid solution of 0.25g0.2M and 0.4000gF127 are dissolved in 6g absolute ethyl alcohol, after stirring, add the phenolic resins ethanolic solution of 0.5200g tetraethoxysilane and 1.25g mass fraction 20% respectively, continue to stir 20min, obtain mixed solution.

Add in above-mentioned mixed solution by the sea urchin shape manganese dioxide 0.1000g of above-mentioned preparation, ultrasonic and stir 3h, at room temperature left standstill volatilization self assembly 5h, put into 100 DEG C, baking oven, insulation 24h, obtains compound.The compound obtained is put into high temperature process furnances, and 900 DEG C of insulation 2h, obtain black product under nitrogen protection.By the black product pulverize obtained, the sodium hydrate aqueous solution putting into concentration 2M stirs 24h, removing silica spheres wherein, then is washed till neutrality with deionized water and absolute ethyl alcohol, obtain manganese dioxide/mesoporous carbon nanometer classification combination electrode material after oven dry, Fig. 2 is its electromicroscopic photograph.

The sign of embodiment 3 manganese dioxide/mesoporous carbon nanometer hierarchical composite material

Use field emission microscope (HITACHIS4800) and nitrogen adsorption desorption (MicromeriticsASAP2020) analyzer manganese dioxide/mesoporous carbon nano composite material to preparation in above-described embodiment 1 and embodiment 2 to carry out the phenetic analysis of surface topography and chemical constitution respectively, result as Fig. 1,2,3 and table 1 shown in.

The electrochemical Characterization of embodiment 4 manganese dioxide/mesoporous carbon nanometer hierarchical composite material

Manganese dioxide embodiment 1 and embodiment 2 prepared/mesoporous carbon nanometer classification combination electrode material, carbon black and polytetrafluoroethylene mixes in mass ratio at 8: 1: 1, adds a small amount of absolute ethyl alcohol, and mixing, stirring, make thick slurry.Get 2 × 1cm 2carbon paper as collector, be coated in equably on carbon paper by the slurry of above-mentioned preparation, area is 1 × 1cm about 2, the baking oven then putting into 70 DEG C is incubated 12 hours.Using the composite electrode sheet of above-mentioned preparation as work electrode, platinized platinum is to electrode, and saturated calomel electrode is reference electrode, and 1M aqueous sodium persulfate solution is that electrolyte is assembled into three electrode test systems, carries out the test of chemical property.Electrochemical workstation PGSTAT302N carries out electrochemical property test, and test voltage interval is-0.1 ~ 0.9V.The electrode material prepared embodiment 1 and embodiment 2 is at 1Ag -1under carry out constant current charge-discharge test, result is as shown in Figure 4.Carry out cyclic voltammetry to electrode material prepared by embodiment 1, result as shown in Figure 5.Carry out cyclical stability test to electrode material prepared by embodiment 1, result as shown in Figure 6.

In embodiment 1, embodiment 2, the physical characteristic of product is as shown in table 1.

Table 1

The ratio capacitance value of electrode material under different current densities of the embodiment 1,2 of preparation can be calculated according to charging and discharging curve.

C=(IΔt)/(mΔV)

The specific capacity of C-active material in formula, Fg -1

The current value of I-constant, A

Δ t-discharge time, s

The quality of active material on m-electrode slice, g

Δ V-discharge voltage is interval, V

Specific capacity (the Fg of combination electrode material under different current density of the embodiment 1,2 utilizing the charging and discharging curve of above-mentioned formula and Fig. 4 to calculate -1) as shown in table 2.

Table 2

Claims (3)

1. a preparation method for manganese dioxide/mesoporous carbon nanometer classification combination electrode material, is characterized in that, comprise the steps:
(1) 0.5 ~ 1.0g Manganous sulfate monohydrate and 0.6 ~ 1.5g ammonium persulfate are successively joined in 45mL deionized water, stir 40 ~ 80min, pour reactor into and reactor is put into baking oven, 8 ~ 12h is kept in the baking oven of 80 ~ 120 DEG C, by the black precipitate deionized water that is obtained by reacting and absolute ethanol washing, dry, obtain the sea urchin shape manganese dioxide with hollow-core construction;
(2) be that the hydrochloric acid solution of 0.2M and 0.05 ~ 0.5g pluronic F127 are dissolved in 3 ~ 8g absolute ethyl alcohol by 0.06 ~ 0.5g concentration, add the ethanolic solution of the phenolic resins of 0.1 ~ 1.0g tetraethoxysilane and 0.3 ~ 2.5g mass fraction 20% after stirring respectively, continue stirring 15 ~ 30min and obtain mixed solution;
Described mass fraction is that in the ethanolic solution of the phenolic resins of 20%, ethanol is solvent;
(3) sea urchin shape manganese dioxide 0.1g step (1) obtained joins in the mixed solution of step (2), stir ultrasonic 2 ~ 4h, then left standstill volatilization self assembly 3 ~ 6h, the baking oven insulation 16 ~ 30h putting into 80 ~ 120 DEG C obtains compound;
(4) compound that step (3) obtains is put into high temperature process furnances, 800 ~ 1000 DEG C of insulation 1 ~ 4h, by the phenolic resin carbonized in compound, obtain black product under nitrogen protection;
(5) black product grinding step (4) obtained, the sodium hydrate aqueous solution putting into concentration 1 ~ 2M stirs 16 ~ 30h, removing silica spheres wherein, neutrality is washed till with a large amount of deionized water and absolute ethyl alcohol, dry, obtain manganese dioxide/mesoporous carbon nanometer classification combination electrode material.
2. preparation method according to claim 1, is characterized in that, in described manganese dioxide/mesoporous carbon nanometer classification combination electrode material, the diameter of manganese dioxide is 1 ~ 5 μm, and surperficial acupuncture length is 500nm ~ 1 μm.
3. preparation method according to claim 1, is characterized in that, described manganese dioxide/mesoporous carbon nanometer classification combination electrode material is applied in ultracapacitor, and its specific capacity exceeds 0.8 ~ 1 times than pure manganese dioxide.
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CN105633373B (en) * 2015-11-06 2018-06-22 北京化工大学 A kind of porous manganese monoxide composite material of carbon coating and its preparation method and application
CN105280393B (en) * 2015-11-24 2017-12-22 华南师范大学 A kind of amorphous carbon material of nano tunnel and preparation method thereof
CN105789608B (en) * 2016-03-29 2019-02-05 华南师范大学 A kind of Si/MnO2The preparation method and application of/graphene/carbon lithium ion battery negative material
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CN106683890A (en) * 2016-11-01 2017-05-17 浙江农林大学 Carbon/manganese oxide composite material, preparation method thereof and application thereof
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