CN102275995A - Method for preparing high-stability nano manganese dioxide powder for water system super capacitor - Google Patents
Method for preparing high-stability nano manganese dioxide powder for water system super capacitor Download PDFInfo
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- CN102275995A CN102275995A CN2011101525060A CN201110152506A CN102275995A CN 102275995 A CN102275995 A CN 102275995A CN 2011101525060 A CN2011101525060 A CN 2011101525060A CN 201110152506 A CN201110152506 A CN 201110152506A CN 102275995 A CN102275995 A CN 102275995A
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Abstract
The invention discloses a method for preparing high-stability nano manganese dioxide powder for a water system super capacitor, which comprises the following steps: (1) preparing manganese dioxide powder by electrochemical deposition; (2) grinding; (3) drying treatment; and (4) performing low-temperature heat treatment. The method has the advantages that: the production process is simple; the production period is short; the equipment cost is low; and the industrialization can be realized easily. The high-stability nano manganese dioxide powder for the water system super capacitor has high stability, has a high specific capacity, has high specific energy and high-stability working window in solution of Na2SO4, K2SO4, Li2SO4 and the like and can be used in power source places with high stability and high power intensity.
Description
Technical field
The present invention relates to a kind of preparation method of manganese dioxide powder, relate in particular to the preparation method of a kind of aqueous super capacitor with the high-stability nano manganese dioxide powder.
Background technology
Along with the technical progress and the industry development of new energy field, energy storage technology more and more is subjected to each side and payes attention to, and becomes the key link that solves the Future New Energy Source industry development, and is current, and ultracapacitor is a kind of technique device of the commercial prospect of tool in the energy storage technology.
Ultracapacitor has broad application prospects in wind energy/solar electric power system and electromobile energy storage field owing to its superior charge-discharge performance and energy-storage property.The main batteries to store energy that adopts in existing wind energy/solar electric power system.Store battery is a kind of simple and convenient, widely used energy storage device, but many deficiencies such as it exists that cycle life is low, high temperature performance is poor, charge and discharge process sensitivity, efficiency for charge-discharge are lower; In the energy source of car field, along with the demand of the sustainability energy and novel energy constantly increases, the application of the vehicles of low emission and zero release becomes trend of the times, and oneself becomes a focus of various countries' research to electric power energy as the main energy sources of automobile.The key component of electromobile is a store battery, the store battery that can be used as the electric powered motor energy has lead-acid cell, nickel metal hydride battery, lithium ion battery and fuel cell etc., though these energy capacity of battery density height, exist the duration of charging long, can't large current charge, shortcoming such as cycle life is short.Comparing the ultracapacitor tool with traditional batteries to store energy equipment has an enormous advantage.Ultracapacitor specific power big (being that store battery is more than 10 times), charge-discharge velocity fast (finishing in denumerable minute), output rating are big, environmental friendliness, capacitor with super capacity have the cycle life more than 100,000 times, and the ultracapacitor battery can works better in-40 ℃～+ 70 ℃ temperature ranges.Therefore ultracapacitor is subjected to paying close attention to widely in the application aspect the energy storage device of wind energy/solar electric power system and electromobile.
The electrode materials that is used for ultracapacitor at present mainly contains: raw material of wood-charcoal material, conducting polymer materials and and metal oxide materials.The raw material of wood-charcoal material is cheap, and its electrode is more higher than electric capacity in the aqueous solution, but that the carbon material electrode exists operating voltage is low, shortcoming such as the specific energy capacity is little; Conductive polymer type electrical condenser biggest advantage is to work under high-voltage, but at present the conductive polymer electrodes material to exist kind few, and have shortcomings such as internal resistance is big, poor stability; Metal oxide type electrical condenser has very high energy density and power density, and common metal oxide electrode material has RuO
2, MnO
2, NiO etc.RuO
2Very higher than electric capacity, be the ideal super capacitor material, but it cost an arm and a leg, contaminate environment and be not easy to obtain.Yet MnO
2Have cheap, chemical property good, toxicity is little, environmentally friendly, advantages such as specific storage is big, become the research focus of electrode material for super capacitor in recent years, though the manganese dioxide powder electrode materials has so many advantage, but still there is the problem of stability in the super electrode capacitor of common manganese dioxide powder material preparation, through after the discharging and recharging more repeatedly, it all can occur significantly decaying than electric capacity and power density etc., shows great unstable.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of aqueous super capacitor with the high-stability nano manganese dioxide powder, present method adopts the anodic electrodeposition method to prepare high-purity block Manganse Dioxide, utilizing mechanical milling method that it is carried out nanometer then handles, adding dispersion agent in the process of lapping prevents to reunite, add grinding aid and improve mill efficiency, the even size distribution of the manganese dioxide powder after the grinding, powder diameter can reach 100～500 nanometers, well satisfies required heavy body, the high-stability requirement of preparation aqueous super capacitor electrode.
The present invention is achieved like this, and method steps is:
(1) electrochemical deposition prepares manganese dioxide powder:
A. pre-treatment: at first the titanium plate is carried out sandblasting, use 30～80g/L NaOH solution washing titanium plate then, remove the greasy dirt on titanium plate surface, then the sulfuric acid of the titanium plate being put into massfraction 15%～50% soaks 1～10h, after being intense violet color, takes out solution sample with the further etching of the vitriol oil at last, flushing is dried, 80 ℃ of etching temperatures, and the time is 1.5h;
B. adopt thermal decomposition method coating sintering IrO on the pretreated titanium plate of process
2The middle layer: compound concentration is 0.10～0.50 moldm
-3The chloro-iridic acid isobutanol solution is coating liquid, coating liquid is coated on the titanium plate of handling well, place 50～100 ℃ of oven dry 5～30min in the baking oven again, 300～600 ℃ of sintering 10～30min in retort furnace then, take out air cooling, repeat 3～10 times, last 300～600 ℃ of sintering 40～90min obtain uniform titanium base IrO
2The middle layer;
C. electrochemical deposition activated manganese dioxide coating: its concrete steps are: at first MnSO
4H
2O, MnCl
2Or manganese acetate and H
2SO
4Be after 1:2～1:10 is mixed with the 500ml aqueous solution solution to be heated to 80～100 ℃ in molar ratio, more packaged sample be placed in one, the logical galvanic current of going up, current density is 2～60 mA/cm
2, galvanic deposit is taken out after 1～5 day to clean and is dried, and separates block MnO on the titanium matrix
2, carry out subsequent disposal then;
(2) grind: the block Manganse Dioxide of electrochemical deposition preparation is placed grinding pot, grinding medium is selected different Stainless Steel Ball of diameter or agate ball for use, ratio of grinding media to material is 2:1～50:1, add sodium polyacrylate or poly carboxylic acid sodium as dispersion agent, dispersant dosage is to account for 0.1%～10% of gross weight, and dispersion agent can be adsorbed on MnO
2Powder particle surface also produces electrostatic repulsion and makes it to disperse, and prevents nanometer MnO
2Powder particle is reunited, and adds ethylene glycol or propylene glycol as grinding aid, and the consumption of grinding aid is to account for 0.1%～30% of gross weight, grinding aid can improve mill efficiency, reduce energy consumption, grind 50～1000 rev/mins of rotating speeds, milling time was controlled at 1～24 hour;
(3) drying treatment: the manganese dioxide powder after will grinding will be put into the loft drier freeze-day with constant temperature, drying temperature: 40～80 ℃; Time of drying 1～24h;
(4) low-temperature heat treatment: the manganese dioxide powder that freeze-day with constant temperature is crossed is put into chamber type electric resistance furnace and is carried out low-temperature heat treatment, thermal treatment temp: 200～500 ℃, and heat treatment time: 1～24h; Thermal treatment finishes and promptly obtains the nano-manganese dioxide powder of aqueous super capacitor with high stability, height ratio capacity and excellent conductive capability.
Technique effect of the present invention is: production technique is simple, and is with short production cycle, and equipment cost is low, is easy to realize industrialization.The aqueous super capacitor of the present invention's preparation has satisfactory stability with the high-stability nano manganese dioxide powder, and very high ratio electric capacity is at Na
2SO
4, K
2SO
4, Li
2SO
4In solution, have the operation window of high-energy-density and high stable, can be applicable to the power supply occasion of high stability, high power density.
Description of drawings
The cyclic voltammetry scan figure (5mV/s) of Fig. 1 embodiment of the invention 1.
The constant current charge-discharge figure (50mA/g) of Fig. 2 embodiment of the invention 1.
The specific storage of Fig. 3 embodiment of the invention 1 and number of cycles graph of a relation.
The MnO of Fig. 4 embodiment of the invention 1
2-AC hybrid super capacitor constant current charge-discharge curve (100mA/g).
The MnO of Fig. 5 embodiment of the invention 1
2The specific storage of-AC hybrid super capacitor and number of cycles graph of a relation.
The MnO of Fig. 6 embodiment of the invention 1
2The field emission scanning electron microscope figure of powder.
The cyclic voltammetry scan figure (5mV/s) of Fig. 7 embodiment of the invention 2.
The constant current charge-discharge figure (50mA/g) of Fig. 8 embodiment of the invention 2.
The specific storage of Fig. 9 embodiment of the invention 2 and number of cycles graph of a relation.
The MnO of Figure 10 embodiment of the invention 2
2-AC hybrid super capacitor constant current charge-discharge curve (100mA/g)
The MnO of Figure 11 embodiment of the invention 2
2The specific storage of-AC hybrid super capacitor and number of cycles graph of a relation.
The MnO of Figure 12 embodiment of the invention 2
2The field emission scanning electron microscope figure of powder.
The cyclic voltammetry scan figure (5mV/s) of Figure 13 embodiment of the invention 3.
The constant current charge-discharge figure (50mA/g) of Figure 14 embodiment of the invention 3.
The specific storage of Figure 15 embodiment of the invention 3 and number of cycles graph of a relation.
The MnO of Figure 16 embodiment of the invention 3
2-AC hybrid super capacitor constant current charge-discharge curve (100mA/g)
The MnO of Figure 17 embodiment of the invention 3
2The specific storage of-AC hybrid super capacitor and number of cycles graph of a relation.
The MnO of Figure 18 embodiment of the invention 3
2The field emission scanning electron microscope figure of powder.
Embodiment
Shown in Fig. 1,2,3,4,5,6,
1. electrochemical deposition prepares MnO
2Powder:
A. adopt thermal decomposition method coating sintering IrO on treated titanium plate
2The middle layer.Compound concentration is 0.1moldm
-3The chloro-iridic acid isobutanol solution is coating liquid, and coating liquid is coated on the titanium plate of handling well, places 70 ℃ of oven dry 20min in the baking oven again, and 300 ℃ of sintering 10min in retort furnace take out air cooling then.Triplicate, last 500 ℃ of sintering 40min obtain uniform titanium base IrO
2The middle layer.
B. the active MnO of electrochemical deposition
2Coating.Its concrete steps are: at first anhydrous Na
2SO
4With H
2SO
4For 2:5 is heated to 70 ℃ with solution after being mixed with the 500ml aqueous solution, more packaged sample is placed in one in molar ratio, (current density is 50mA/cm can to lead to galvanic current afterwards
2).Galvanic deposit is taken out after 3 days to clean and is dried, and peels off block MnO on the titanium matrix
2
2. grind (amount of grinding is 50g): electrochemical deposition is prepared block MnO
2Put into grinding pot, grinding medium be different diameter agate ball (6mm, 10mm), ratio of grinding media to material 15:1 adds sodium polyacrylate (consumption is 1%), grinding aid ethylene glycol or propylene glycol (consumption is 0.1%), 300 rev/mins of grinding rates, milling time 5 hours;
3. drying treatment: after the to be ground jar of cooling with MnO
2Powder takes out dry, time of drying: 24h, drying temperature: 60 ℃;
4. low-temperature heat treatment: the MnO that drying is finished
2Powder is done low-temperature heat treatment, and thermal treatment temp is 400 ℃, and the time is 4h;
5. electrode preparation: with nanometer MnO
2Powder, acetylene black, PTEF prepare electrode of super capacitor by the mass ratio of 65:20:15;
6. manganese dioxide powder powder electrode material cyclic voltammetric test: scanning speed is 5 mV/s, and working electrode is a manganese dioxide electrode, and reference electrode is a saturated calomel electrode, and supporting electrode is the Pt electrode, and electrolytic solution is 0.5mol/L Na
2SO
4
7. the constant current charge-discharge of electrode and stability test: positive and negative electrode is manganese dioxide electrode, and current density is 50 mA/g, and operating voltage is 0～0.8V.After 60000 circulations, capacity attenuation 8.51%, electrode is stable.
8. MnO
2-AC hybrid super capacitor constant current charge-discharge stabilizer pole property testing: manganese dioxide electrode just very, negative pole is two activated carbon electrodes, and current density is 100 mA/g, and operating voltage is 0～2V.After 39500 circulations, capacity attenuation 7.82%, electrode is stable.
Embodiment 2
Shown in Fig. 7,8,9,10,11,12,
1. electrochemical deposition prepares MnO
2Powder:
A. adopt thermal decomposition method coating sintering IrO on treated titanium plate
2The middle layer.Compound concentration is 0.3moldm
-3The chloro-iridic acid isobutanol solution is coating liquid, and coating liquid is coated on the titanium plate of handling well, places 80 ℃ of oven dry 20min in the baking oven again, and 350 ℃ of sintering 10min in retort furnace take out air cooling then.Triplicate, last 550 ℃ of sintering 40min obtain uniform titanium base IrO
2The middle layer.
B. the active MnO of electrochemical deposition
2Coating.Its concrete steps are: at first anhydrous Na
2SO
4With H
2SO
4For 2:5 is heated to 75 ℃ with solution after being mixed with the 500ml aqueous solution, more packaged sample is placed in one in molar ratio, (current density is 40mA/cm can to lead to galvanic current afterwards
2).Galvanic deposit is taken out after 3 days to clean and is dried, and peels off block MnO on the titanium matrix
2
2. grind (amount of grinding is 100g): electrochemical deposition is prepared block MnO
2Put into grinding pot, grinding medium is agate ball (6mm, the 8mm of different diameter, 10mm), ratio of grinding media to material 10:1 adds sodium polyacrylate (consumption is 2%), grinding aid ethylene glycol or propylene glycol (consumption is 20%), 500 rev/mins of grinding rates, milling time 6 hours;
3. drying treatment: after the to be ground jar of cooling with MnO
2Powder takes out dry, time of drying: 24h, drying temperature: 60 ℃;
4. low-temperature heat treatment: the MnO that drying is finished
2Powder is done low-temperature heat treatment, and thermal treatment temp is 420 ℃, and the time is 4h;
5. electrode preparation: with nanometer MnO
2Powder, acetylene black, PTEF prepare electrode of super capacitor by the mass ratio of 65:20:15;
6. manganese dioxide powder powder electrode material cyclic voltammetric test: scanning speed is 5 mV/s, and working electrode is a manganese dioxide electrode, and reference electrode is a saturated calomel electrode, and supporting electrode is the Pt electrode, and electrolytic solution is 0.5mol/L Na
2SO
4
7. the constant current charge-discharge of electrode and stability test: positive and negative electrode is manganese dioxide electrode, and current density is 50 mA/g, and operating voltage is 0～0.8V.After 60000 circulations, capacity attenuation 12.70%, electrode is stable.
8. MnO
2-AC hybrid super capacitor constant current charge-discharge stabilizer pole property testing: manganese dioxide electrode just very, negative pole is two activated carbon electrodes, and current density is 100 mA/g, and operating voltage is 0～2V.Capacity attenuation 7.67% after 39500 circulations, electrode is stable.
Embodiment 3
Shown in Figure 13,14,15,16,17,18,
1. electrochemical deposition prepares MnO
2Powder:
A. adopt thermal decomposition method coating sintering IrO on treated titanium plate
2The middle layer.Compound concentration is 0.3moldm
-3The chloro-iridic acid isobutanol solution is coating liquid, and coating liquid is coated on the titanium plate of handling well, places 70 ℃ of oven dry 20min in the baking oven again, and 400 ℃ of sintering 10min in retort furnace take out air cooling then.Triplicate, last 500 ℃ of sintering 40min obtain uniform titanium base IrO
2The middle layer.
B. the active MnO of electrochemical deposition
2Coating.Its concrete steps are: at first anhydrous Na
2SO
4With H
2SO
4For 2:5 is heated to 80 ℃ with solution after being mixed with the 500ml aqueous solution, more packaged sample is placed in one in molar ratio, (current density is 30mA/cm can to lead to galvanic current afterwards
2).Galvanic deposit is taken out after 3 days to clean and is dried, and peels off block MnO on the titanium matrix
2
2. grind (amount of grinding is 200g): electrochemical deposition is prepared block MnO
2Put into grinding pot, grinding medium is agate ball (6mm, the 8mm of different diameter, 10mm), ratio of grinding media to material 10:1 adds sodium polyacrylate (consumption is 5%), grinding aid ethylene glycol or propylene glycol (consumption is 10%), 600 rev/mins of grinding rates, milling time 8 hours;
3. drying treatment: after the to be ground jar of cooling with MnO
2Powder takes out dry, time of drying: 24h, drying temperature: 80 ℃;
4. low-temperature heat treatment: the MnO that drying is finished
2Powder is done low-temperature heat treatment, and thermal treatment temp is 400 ℃, and the time is 4h;
5. electrode preparation: with nanometer MnO
2Powder, acetylene black, PTEF prepare electrode of super capacitor by the mass ratio of 65:20:15;
6. manganese dioxide powder powder electrode material cyclic voltammetric test: scanning speed is 5 mV/s, and working electrode is a manganese dioxide electrode, and reference electrode is a saturated calomel electrode, and supporting electrode is the Pt electrode, and electrolytic solution is 0.5mol/L Na
2SO
4
7. the constant current charge-discharge of electrode and stability test: positive and negative electrode is manganese dioxide electrode, and current density is 50 mA/g, and operating voltage is 0～0.8V.After 60000 circulations, capacity attenuation 13.73%, electrode is stable.
8. MnO
2-AC hybrid super capacitor constant current charge-discharge stabilizer pole property testing: manganese dioxide electrode just very, negative pole is two activated carbon electrodes, and current density is 100 mA/g, and operating voltage is 0～2V.After 39500 circulations, capacity attenuation 7.64%, electrode is stable.
Claims (1)
1. an aqueous super capacitor is characterized in that method steps is with the preparation method of high-stability nano manganese dioxide powder:
(1) electrochemical deposition prepares manganese dioxide powder:
A. pre-treatment: at first the titanium plate is carried out sandblasting, use 30～80g/L NaOH solution washing titanium plate then, remove the greasy dirt on titanium plate surface, then the sulfuric acid of the titanium plate being put into massfraction 15%～50% soaks 1～10h, after being intense violet color, takes out solution sample with the further etching of the vitriol oil at last, flushing is dried, 80 ℃ of etching temperatures, and the time is 1.5h;
B. adopt thermal decomposition method coating sintering IrO on the pretreated titanium plate of process
2The middle layer: compound concentration is 0.10～0.50 moldm
-3The chloro-iridic acid isobutanol solution is coating liquid, coating liquid is coated on the titanium plate of handling well, place 50～100 ℃ of oven dry 5～30min in the baking oven again, 300～600 ℃ of sintering 10～30min in retort furnace then, take out air cooling, repeat 3～10 times, last 300～600 ℃ of sintering 40～90min obtain uniform titanium base IrO
2The middle layer;
C. electrochemical deposition activated manganese dioxide coating: its concrete steps are: at first MnSO
4H
2O, MnCl
2Or manganese acetate and H
2SO
4Be after 1:2～1:10 is mixed with the 500ml aqueous solution solution to be heated to 80～100 ℃ in molar ratio, more packaged sample be placed in one, the logical galvanic current of going up, current density is 2～60 mA/cm
2, galvanic deposit is taken out after 1～5 day to clean and is dried, and separates block MnO on the titanium matrix
2, carry out subsequent disposal then;
(2) grind: the block Manganse Dioxide of electrochemical deposition preparation is placed grinding pot, grinding medium is selected different Stainless Steel Ball of diameter or agate ball for use, ratio of grinding media to material is 2:1～50:1, add sodium polyacrylate or poly carboxylic acid sodium as dispersion agent, dispersant dosage is to account for 0.1%～10% of gross weight, and dispersion agent can be adsorbed on MnO
2Powder particle surface also produces electrostatic repulsion and makes it to disperse, and prevents nanometer MnO
2Powder particle is reunited, and adds ethylene glycol or propylene glycol as grinding aid, and the consumption of grinding aid is to account for 0.1%～30% of gross weight, grinding aid can improve mill efficiency, reduce energy consumption, grind 50～1000 rev/mins of rotating speeds, milling time was controlled at 1～24 hour;
(3) drying treatment: the manganese dioxide powder after will grinding will be put into the loft drier freeze-day with constant temperature, drying temperature: 40～80 ℃; Time of drying 1～24h;
(4) low-temperature heat treatment: the manganese dioxide powder that freeze-day with constant temperature is crossed is put into chamber type electric resistance furnace and is carried out low-temperature heat treatment, thermal treatment temp: 200～500 ℃, and heat treatment time: 1～24h; Thermal treatment finishes and promptly obtains the nano-manganese dioxide powder of aqueous super capacitor with high stability, height ratio capacity and excellent conductive capability.
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| CN103265082A (en) * | 2013-06-19 | 2013-08-28 | 南昌航空大学 | Preparation method of three-dimensional manganese dioxide nano net |
| CN103346027A (en) * | 2013-07-08 | 2013-10-09 | 山东大学 | Supercapacitor material manufacturing technology based on nano-porous titanium skeleton |
| CN104971802A (en) * | 2015-05-22 | 2015-10-14 | 广西有色金属集团汇元锰业有限公司 | Nanometer bead milling system and nanocrystalline microsphere preparation method |
| CN104988528A (en) * | 2015-05-27 | 2015-10-21 | 广西有色金属集团汇元锰业有限公司 | Method for producing electrolytic manganese dioxide by using nanocrystalline microsphere modified electrode |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265082A (en) * | 2013-06-19 | 2013-08-28 | 南昌航空大学 | Preparation method of three-dimensional manganese dioxide nano net |
| CN103346027A (en) * | 2013-07-08 | 2013-10-09 | 山东大学 | Supercapacitor material manufacturing technology based on nano-porous titanium skeleton |
| CN103346027B (en) * | 2013-07-08 | 2016-06-08 | 山东大学 | The preparation technology of a kind of super capacitor material based on nanoporous titanium skeleton |
| CN104971802A (en) * | 2015-05-22 | 2015-10-14 | 广西有色金属集团汇元锰业有限公司 | Nanometer bead milling system and nanocrystalline microsphere preparation method |
| CN104971802B (en) * | 2015-05-22 | 2017-11-03 | 广西有色金属集团汇元锰业有限公司 | A kind of preparation method of nano-beads grinding system and nano-crystalline microsphere |
| CN104988528A (en) * | 2015-05-27 | 2015-10-21 | 广西有色金属集团汇元锰业有限公司 | Method for producing electrolytic manganese dioxide by using nanocrystalline microsphere modified electrode |
| CN104988528B (en) * | 2015-05-27 | 2017-10-13 | 广西有色金属集团汇元锰业有限公司 | Method for producing electrolytic manganese dioxide by using nanocrystalline microsphere modified electrode |
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| Publication number | Publication date |
|---|---|
| CN102275995B (en) | 2013-07-03 |
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