CN106971858B - A kind of preparation method of manganese dioxide/carbon combination electrode material - Google Patents
A kind of preparation method of manganese dioxide/carbon combination electrode material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of manganese dioxide/carbon combination electrode material.Preparation method of the present invention includes the following steps: that carbon material is put into and is surface-treated containing sugared mixed solution by 1., adsorbs glycan molecule sufficiently on its surface；2. the carbon material after surface treatment is heat-treated, makes the saccharide part on its surface that dehydrating polycondensation, melting and solidification occur, obtain to surface and be evenly distributed with the carbon material of hydroxyl；3. the carbon material that surface is evenly distributed with hydroxyl is reacted with MnO4 and/or mangaic acid root, manganese dioxide/carbon combination electrode material is obtained.The present invention in carbon material surface by coating and solidifying sugar, and makes it that in-situ oxidation reduction reaction occur in carbon material surface with MnO4 and/or mangaic acid root and generate manganese dioxide, to make manganese dioxide and two kinds of components of carbon material in composite material come into full contact with to improve the ionic conductivity of material, the capacitive property of material is improved.Preparation process of the present invention and equipment requirement are simple, are convenient for industrial production.
Description
Technical field
The present invention relates to a kind of preparation methods of manganese dioxide/carbon combination electrode material；Belong to electrochemical technology field.
Technical background
Supercapacitor is a kind of new concept energy storage device between battery and conventional electrostatic container, with aluminium electricity
The conventional electrostatics capacitor such as electrolysis condenser is compared, and supercapacitor has higher specific capacitance, and storable energy density is to pass
10 times or more of system electrostatic condenser；And compared with battery, supercapacitor has bigger power density, and has charge and discharge
It is high-efficient, the characteristics such as have extended cycle life.Due to having above many superiority, the exploitation of supercapacitor technologies is constantly subjected to
Academia, industrial circle and military service most attention, and gradually in electronic instrument backup power supply and rocket, guided missile, artificial
It is applied in terms of the point starting ignition power supply of satellite, spaceship space station etc., the super high power electricity of wherein starting ignition
Container can provide MW grades of especially big startup power.
The decision most important factor of capacitor chemical property is the electrode material used in it.Currently, being widely used as surpassing
The material of grade electrode for capacitors active material includes carbon material, conducting polymer and transition metal oxide material.In transition gold
Belong in oxide, ruthenium-oxide is a kind of electrode material of electrochemical performance, is had in the electrolyte system of aqueous sulfuric acid
There are higher specific capacity, good electric conductivity and stability.However, its is at high cost, there is toxicity, and electrolyte has corruption
Corrosion, environment easy to pollute.These defects make it be difficult to realize be commercialized popularization and application on a large scale, can only be in certain national defences
It is used.For the metal oxide containing precious metals as the ruthenium-oxide, MnO2、NiO、FeOx、V2O5Equal base metal oxides by
It is resourceful in cheap, have what is promoted and applied to have a extensive future.In these oxides, MnO2Theoretical specific capacitance
1370F g can be reached-1, good electrochemical properties and current potential can be shown in neutral aqueous electrolyte as electrode material
Window is wider, is a kind of very promising electrode material.
However, the ionic conductivity of pure manganese dioxide poor (general 10-4-10-6S cm-1) cause its specific capacitance and multiplying power special
Property is all unsatisfactory and can not promote and apply.In order to obtain ideal capacitance material, by manganese dioxide and there is good electricity
The compound carbon material of sub- conductance property is the hot spot studied recently, i.e., provides higher electroactive area and reliable by carbon material
Conductive path improve MnO2Performance.Prepared manganese dioxide and various carbon materials, including active carbon (AC), carbon nanometer
The composite material of pipe, mesoporous carbon, carbon black, graphene etc. has shown preferable capacitive property.Preparation side involved at present
Method mainly includes that powder is blended, and carbon material is added when preparing manganese dioxide by oxidation-reduction method in aqueous solution, in carbon material
Pass through again after preparing carbon fiber or carbon nano pipe array by vapor deposition load manganese dioxide or by vapor deposition on matrix
Electrochemical process is in these carbon material surfaces deposition manganese dioxide etc..It is blended by powder, and prepares manganese dioxide in chemical method
When carbon material is added into solution method be difficult to ensure coming into full contact with for manganese dioxide and carbon material in gained composite material, shadow
Ring the performance of material capacitive property.And the rule that is vapor-deposited still has some deficits on preparation cost.It is answered in order to make to prepare
Manganese dioxide can come into full contact with carbon material in condensation material, first carbon material is carried out aoxidizing in oxyacid and and bivalent manganese
Reacting again with potassium permanganate etc. after grafting is a kind of effective method, but this method still has preparation process relative complex, preparation
The deficiencies of strong acid reaction under high pressure link in the process is harsh to equipment requirement.Therefore, seek new material preparation method to overcome
The above problem is necessary.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of process equipments to require simple, low in cost, manganese dioxide point
Dissipate uniformly and contact with carbon material the preparation method of sufficient manganese dioxide/carbon combination electrode material.
A kind of preparation method of manganese dioxide/carbon composite material of the present invention, includes the following steps:
Step 1
Carbon material and the mixed aqueous solution containing A are mixed, are separated by solid-liquid separation, it is dry, obtain the carbon material that adsorption has A；
The A is carbohydrate；
Step 2
At 150~240 DEG C, there is the carbon material of A to be heat-treated the resulting adsorption of step 1, it is uniform to obtain surface
The carbon material of hydroxyl is distributed with；
Step 3
The carbon material that surface is evenly distributed with hydroxyl is put into the solution containing MnO4 and is reacted, it is solid after reaction
Solid phase is cleaned in liquid separation, dry, obtains manganese dioxide/carbon composite material.
A kind of preparation method of manganese dioxide/carbon combination electrode material of the present invention, carbohydrate described in step 1 be selected from ribose,
One or more of xylose, arabinose, glucose, fructose, sucrose, maltose, Soluble Fiber.
A kind of preparation method of manganese dioxide/carbon combination electrode material of the present invention, in step 1 in the mixed aqueous solution containing A
Also contain polyacid, the polyacid includes including one or both of citric acid, tartaric acid.
A kind of preparation method of manganese dioxide/carbon combination electrode material of the present invention, the mixing described in step 1 containing A are water-soluble
Also contain polyalcohol in liquid, the polyalcohol includes one or more of xylitol, mannitol and callery pear flower alkyd.
A kind of preparation method of manganese dioxide/carbon combination electrode material of the present invention, the mixing described in step 1 containing A are water-soluble
The concentration of A is 0.1~0.5mol/L in liquid；
When containing polyacid in the mixed aqueous solution containing A, polyacid quality is the 1%~5% of A mass；
When containing polyalcohol in the mixed aqueous solution containing A, the quality of polyalcohol is the 10%~30% of A mass.
Preferably, a kind of preparation method of manganese dioxide/carbon combination electrode material of the present invention, the carbon material choosing
From carbon nanotube, carbon fiber, carbon black, at least one of graphene.
Preferably, matched by every gram of carbon material using 20~100mL of mixed aqueous solution and take carbon material and containing the mixing of A
Aqueous solution.
A kind of preparation method of manganese dioxide/carbon combination electrode material of the present invention, in step 2 heat treatment temperature be 150~
240 DEG C, heat treatment time is 1~5 hour.When heat treatment, part dehydrating polycondensation occurs for the sugar of carbon material surface, solidifies after melting
In carbon material surface.
A kind of preparation method of manganese dioxide/carbon combination electrode material of the present invention, the surface obtained by step 2 are uniformly distributed
There is carbon material used in the carbon material alternative steps one of hydroxyl, repeats Step 1: step 22 times or more；Then step is carried out again
Three operation.It repeats Step 1: step 22 times or more to increase the adsorbance of carbon material surface sugar.Duplicate number is preferred
It is 2-8 times, further preferably 2-6 times.
A kind of preparation method of manganese dioxide/carbon combination electrode material of the present invention, in step 3, in step 3, the height
Mangaic acid root is provided by permanganic acid or permanganate；The permanganate in potassium permanganate, sodium permanganate, high manganese lithium extremely
Few one kind.Preferably, the MnO4 is provided by permanganate.
A kind of preparation method of manganese dioxide/carbon combination electrode material of the present invention, in step 3, when reaction, control reaction
Temperature be room temperature to 60 DEG C, reaction time be 6h~for 24 hours.
A kind of preparation method of manganese dioxide/carbon combination electrode material of the present invention, prepared composite material can be used for surpassing
Grade electrode for capacitors.
Principle and advantage
The present invention handles carbon material using a kind of mixed solution containing sugar first, inhales carbon material surface by adsorption
Attached sugar, and through Overheating Treatment make saccharide part occur polycondensation and solidify and carbon material surface, be finally soaked in root containing mangaic acid and/
Or in the solution of MnO4, pass through mangaic acid root and/or a large amount of hydroxyl of MnO4 oxidized surface；In carbon material surface original position
Generate manganese dioxide.
As a preferred solution of the present invention, by carbon material surface uniform adsorption sugar, (sugar includes raw material institute to the present invention
Sugar and raw material hydrolysis the gained sugar of introducing) and part polyalcohol and polyacid, and promote these sugar that can consolidate by heat treatment
Change in carbon material surface, makes carbon material surface uniform fold great amount of hydroxy group group.After mangaic acid root and/or MnO4 is added,
These hydroxyls and coupled carbon atom are oxidized to carbon dioxide and water by mangaic acid root and/or MnO4, mangaic acid root and/or
MnO4 is then reduced into manganese dioxide in carbon material surface, enables the manganese dioxide uniform fold generated on carbon material,
To ensure that coming into full contact with for manganese dioxide and carbon material, to improve the capacitive property of material.
The present invention and it is existing carbon material is added when preparing manganese dioxide by oxidation-reduction method in aqueous solution, prepare dioxy
Change manganese/carbon composite technology, which compares, to be had the advantage that
1. in composite material prepared by the present invention, carbon material contacts more abundant with manganese dioxide；
2. in composite material prepared by the present invention, the distribution of manganese dioxide is more uniform；It is not in the prior art
The phenomenon that manganese dioxide local accumulation easily occurred, carbon material surface in the prior art will not occurs and bottom pour ladle two easily occurs
The phenomenon that manganese oxide；
3. the present invention compared with using the technique of strong acid treatment carbon material, have it is at low cost, be easy to operate and control, to setting
It is standby of less demanding, convenient for originating in industrialization production and promoting.
Detailed description of the invention
Attached drawing 1 is that the circulation using manganese dioxide/carbon combination electrode prepared by the embodiment of the present invention 1 at 2mV/s lies prostrate
Pacify curve graph, specific capacitance of the electrode material at 2mV/s can be calculated according to the curve.
Specific embodiment
In order to detect the performance of gained composite material, in the embodiment of the present invention and comparative example, generally by products obtained therefrom
Pole piece is made by following methods:
Gained composite material and conductive agent conductive black, bonding agent PVDF are sufficiently mixed in 75: 15: 10 ratio, put
Enter solvent NMP and is prepared into slurry.Slurry is coated in 1 × 1cm nickel foam, is put into 80 DEG C of dryings in vacuum oven, and
Pole piece is pressed under 10MPa pressure.
After pole piece is made, its performance, the environment and condition of detection are detected are as follows:
It is to electrode with Pt electrode, saturation Mercurous sulfate electrode is reference electrode, 0.5mol L-1Metabisulfite solution be electricity
Liquid is solved, three-electrode system is formed, carries out cyclic voltammetry, test potential range is -0.4~0.4V, sweep speed 2mV/
s。
Embodiment 1
The mixed aqueous solution 100mL containing sucrose, citric acid and mannitol is prepared, wherein sucrose concentration is 0.5mol/L, lemon
The content of lemon acid and mannitol is respectively the 5% and 10%. of cane sugar content (weight) carbon nanotube to be added into the mixed solution
(CNT, size are as follows: average diameter 7nm, average length 6m) 0.5g, is filtered after being stirred at room temperature 3 hours, is put again after dry, grinding
Enter in Muffle furnace and handle 1 hour for 240 DEG C, obtains the carbon of surface uniform fold sucrose, sucrose hydrolysis product, citric acid, mannitol
Nanotube.
The carbon nanotube that above-mentioned surface is covered with sucrose, sucrose hydrolysis product, citric acid and mannitol, which is put into concentration, is
The KMnO of 0.2mol/L4Solution simultaneously moves in water-bath, continuously stirs 12h at 60 DEG C.Object cooled to room temperature to be mixed, very
Empty pump filters and be washed with deionized filter cake until filtrate is in colourless (pH value of washing lotion is 7).Filter cake obtains after drying, grinding
MnO2/ CNT composite material；
By MnO2/ CNT composite material and conductive agent conductive black, bonding agent PVDF are sufficiently mixed in 75: 15: 10 ratio
It closes, is put into solvent NMP and is prepared into slurry.Slurry is coated in 1 × 1cm nickel foam, 80 DEG C of dryings in vacuum oven are put into,
And pole piece is pressed under 10MPa pressure.It is to electrode with Pt electrode, saturation Mercurous sulfate electrode is reference electrode, 0.5mol
L-1Metabisulfite solution be electrolyte, form three-electrode system, carry out cyclic voltammetry, test potential range be -0.4~
0.4V, sweep speed 2mV/s, the specific capacitance for measuring material is 321.4F/g.
Embodiment 2
Experimentation is same as Example 1, only replaces sucrose, concentration of glucose 0.1mol/L, lemon with glucose
The dosage of acid and mannitol is respectively the 1% and 20% of glucose content (weight), and immersion-drying steps heat treatment temperature is
150 DEG C, the processing time is 3 hours, and immersion-drying-heat treatment is repeated 3 times, and surface is covered with to the carbon nanotube of glucose
Being put into the temperature reacted in liquor potassic permanganate is room temperature, and the time is 24 hours.Test gained composite material specific capacitance be
311.1F/g。
Embodiment 3
Experimentation is same as Example 1, only replaces sucrose with arabinose, arabinose concentrations 0.2mol/L,
The dosage of citric acid and mannitol is respectively the 1% and 20% of arabinose content (weight), and heat treatment temperature is 180 DEG C, place
Managing the time is 2 hours, and immersion-drying-heat treatment is repeated 3 times, and the carbon nanotube that surface is covered with arabinose is put into height
The temperature reacted in potassium manganate solution is 40 DEG C, and the time is 10 hours.The specific capacitance of test gained composite material is 338.9F/g.
Embodiment 4
Experimentation is same as Example 1, only replaces sucrose with fructose, and fructose concentration 0.2mol/L uses tartaric acid
Citric acid and mannitol are replaced with xylitol, the dosage of tartaric acid and xylitol is respectively 3% He of fructose content (weight)
12%, heat treatment temperature is 190 DEG C, and the processing time is 2 hours, and immersion-drying-heat treatment is repeated 6 times, and surface is covered with fruit
It is 40 DEG C that the carbon nanotube of sugar, which is put into the temperature reacted in liquor potassic permanganate, and the time is 10 hours.Test gained composite wood
The specific capacitance of material is 328.9F/g.
Embodiment 5
Experimentation is same as Example 1, only replaces sucrose with maltose, and maltose concentration 0.15mol/L uses wine
Stone acid and xylitol replace citric acid and mannitol, and the dosage of tartaric acid and xylitol is respectively maltose content (weight)
1.5% and 15%, heat treatment temperature is 220 DEG C, and the processing time is 2 hours, and immersion-drying-heat treatment is repeated 2 times, by surface
It is 40 DEG C that the carbon nanotube for being covered with maltose, which is put into the temperature reacted in liquor potassic permanganate, and the time is 10 hours.Test
The specific capacitance of gained composite material is 308.9F/g.
Comparative example 1
CNT, glucose and potassium permanganate are weighed in the ratio of embodiment 1 and are uniformly mixed, is moved in water-bath, at 60 DEG C
Continuously stir 12h.Object cooled to room temperature to be mixed is filtered by vacuum and is washed with deionized filter cake until filtrate is in nothing
Color.Filter cake obtains MnO after drying, grinding2/ CNT composite material.It is active material according to embodiment one with the composite material
Method prepares electrode and carries out cyclic voltammetry, and measuring specific capacitance of the gained composite material at 2mV/s is 214F/g.
Comparative example 2
Other uniform embodiments 1 of condition are completely the same, the difference is that substituting citric acid using oxalic acid；Products obtained therefrom
Specific capacitance be 223F/g.
Claims (10)
1. a kind of preparation method of manganese dioxide/carbon combination electrode material, which is characterized in that include the following steps:
Step 1
Carbon material and the mixed aqueous solution containing A are mixed, are separated by solid-liquid separation, it is dry, obtain the carbon material that adsorption has A；The A
For carbohydrate；
Step 2
At 150~240 DEG C, there is the carbon material of A to be heat-treated the resulting adsorption of step 1, obtain to surface and be uniformly distributed
There is the carbon material of hydroxyl；
Step 3
The carbon material that surface is evenly distributed with hydroxyl is put into the solution containing MnO4 and is reacted, solid-liquid point after reaction
From, solid phase is cleaned, it is dry, obtain manganese dioxide/carbon composite material.
2. a kind of preparation method of manganese dioxide/carbon combination electrode material according to claim 1, it is characterised in that: step
Carbohydrate described in rapid one in ribose, xylose, arabinose, glucose, fructose, sucrose, maltose, Soluble Fiber one
Kind is several.
3. a kind of preparation method of manganese dioxide/carbon combination electrode material according to claim 1, it is characterised in that: step
Also contain polyacid in mixed aqueous solution containing A described in rapid one, the polyacid include one of citric acid, tartaric acid or
Two kinds.
4. a kind of preparation method of manganese dioxide/carbon combination electrode material according to claim 1, it is characterised in that: step
Also contain polyalcohol in mixed aqueous solution containing A described in rapid one, the polyalcohol includes xylitol, mannitol and callery pear flower alcohol
One or more of acid.
5. a kind of preparation method of manganese dioxide/carbon combination electrode material according to claim 1, it is characterised in that:
The concentration of A is 0.1~0.5mol/L in mixed aqueous solution described in step 1 containing A；
When containing polyacid in the mixed aqueous solution containing A, polyacid quality is the 1%~5% of A mass；
When containing polyalcohol in the mixed aqueous solution containing A, the quality of polyalcohol is the 10%~30% of A mass.
6. a kind of preparation method of manganese dioxide/carbon combination electrode material according to claim 1, it is characterised in that: step
Heat treatment temperature is 150~240 DEG C in rapid two, and heat treatment time is 1~5 hour.
7. a kind of preparation method of manganese dioxide/carbon combination electrode material according to claim 1, it is characterised in that: use
Surface obtained by step 2 is evenly distributed with carbon material used in the carbon material alternative steps one of hydroxyl, repeats Step 1: step 22 times
Or more；Then the operation of step 3 is carried out again.
8. a kind of preparation method of manganese dioxide/carbon combination electrode material according to claim 1, it is characterised in that: step
In rapid three, the MnO4 is provided by permanganic acid or permanganate；The permanganate be selected from potassium permanganate, sodium permanganate,
At least one of high manganese lithium.
9. a kind of preparation method of manganese dioxide/carbon combination electrode material according to claim 1, it is characterised in that: step
In rapid three, when reaction, control reaction temperature be room temperature to 60 DEG C, reaction time be 6h~for 24 hours.
10. a kind of preparation method of manganese dioxide/carbon combination electrode material according to claim 1, it is characterised in that: institute
The composite material of preparation can be used for electrode of super capacitor.
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| CN116062755B (en) * | 2021-10-30 | 2024-06-28 | 中国石油化工股份有限公司 | Activated carbon material loaded with metal oxide and preparation method and application thereof |
| CN114229903B (en) * | 2021-11-23 | 2023-10-31 | 湖北大学 | MnO (MnO) 2 Electrode material, preparation method and application thereof |
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| KR20060061412A (en) * | 2004-12-02 | 2006-06-08 | 현대자동차주식회사 | Method for manufacturing manganese oxide/carbon nanotube composite electrode for super capacitor using electrostatic spary deposition |
| CN103972518A (en) * | 2013-02-05 | 2014-08-06 | 中国科学院大连化学物理研究所 | Manganese dioxide/carbon nanocomposite, and preparation method and application thereof |
| CN104392849A (en) * | 2014-11-20 | 2015-03-04 | 中南大学 | Manganese dioxide/ con composite material preparing method |
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| KR20060061412A (en) * | 2004-12-02 | 2006-06-08 | 현대자동차주식회사 | Method for manufacturing manganese oxide/carbon nanotube composite electrode for super capacitor using electrostatic spary deposition |
| CN103972518A (en) * | 2013-02-05 | 2014-08-06 | 中国科学院大连化学物理研究所 | Manganese dioxide/carbon nanocomposite, and preparation method and application thereof |
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