CN105198006B - The application of porous cobaltosic oxide - Google Patents
The application of porous cobaltosic oxide Download PDFInfo
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- CN105198006B CN105198006B CN201510565368.7A CN201510565368A CN105198006B CN 105198006 B CN105198006 B CN 105198006B CN 201510565368 A CN201510565368 A CN 201510565368A CN 105198006 B CN105198006 B CN 105198006B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a kind of application of porous cobaltosic oxide, porous cobaltosic oxide disclosed by the invention is Porous hollow spheroid shape, specific surface area is higher, hole relatively enriches, and pore size is adjustable, can be used as high-performance super capacitor electrode material, vehicle maintenance service material and sorbing material.
Description
Technical field
The invention discloses a kind of application of porous cobaltosic oxide, belong to inorganic salts porous material applied technical field.
Background technology
With the development of the social economy, people are increasingly paid close attention to ecological environment and green energy resource.One in vehicle exhaust
The pollutants such as carbonoxide, hydrocarbon can cause photochemical fog etc..Therefore, vehicle exhaust is directly discharged in air,
It is huge to environmental hazard, have a strong impact on the life security of people.
Cobaltosic oxide has spinel crystal structure, is a kind of important magnetic material, P-type transition metal oxide,
Peculiar physical and chemical properties are shown in fields such as electricity, magnetic, air-sensitive, catalysis, are widely used in lithium ion cell electrode
The key areas such as material, magnetic material, heterogeneous catalyst, vehicle maintenance service.For example：Cobaltosic oxide may be used as super electricity
The electrode material of container.Ultracapacitor is increasingly subject to pay attention to as a kind of new type of energy storage device.With it is now widely used each
Kind of energy storage material is compared, and ultracapacitor charge/discharge rates and efficiency are better than once or secondary cell.
The physical and chemical properties of cobaltosic oxide are influenceed larger by pattern, size and structure, and then influence it to apply
Performance.In recent years, the cobaltosic oxide material with different-shape causes the great interest of people, using mist projection granulating, micro emulsion
The different preparation method such as liquid reaction method, sol-gel process, vapor deposition method has synthesized nanosphere, nano wire, nanometer in succession
Rod, nanotube, nanofiber, nanocube, hollow ball, flower-like microsphere, garland shape cobaltosic oxide etc..
Chinese patent CN103011306B has invented a kind of method for preparing nanometer-level cube-like cobaltosic oxide, by one
Scattered be added in deionized water, after ultrasonic disperse of quantitative porous carbon fills cobalt salt, urea and deionized water mixed solution
Reactor in, after being thoroughly mixed, reactor is placed in baking oven, hydro-thermal reaction naturally cools to room after certain time
Temperature, reaction product is centrifuged for several times, after water-washing process, obtains cubic cobaltosic oxide powder, the oxygen of cubic four
Porous nano level cubic cobaltosic oxide can further be obtained after high-temperature calcination in atmosphere by changing three cobalt dusts；Chinese patent
CN102887548B has invented a kind of sea-urchin-shaped hiberarchy cobaltosic oxide nanosphere and preparing and preparation method thereof, and cobalt chloride is water-soluble
Liquid is mixed with glycerine, adds urea, and reaction, removal of impurities, calcining obtains sea-urchin-shaped hiberarchy cobaltosic oxide nanosphere and preparing；In
State patent CN101913659B has invented a kind of preparation method of battery-grade cobaltosic oxide, with deionized water is by cobalt raw material and sinks
Shallow lake agent is made into cobalt liquor respectively；Presoma is prepared using even phase crystallized precipitation method；Scrubbed, dehydration directly fills aqueous filter cake
Alms bowl, using low temperature dewatering phase transformation calcination again by high temperature nodularization calcining control grain size and crystal morphology；Then through mechanical crushing
It is classified activation process；The removal of magnetic metal foreign matter is finally carried out, spherical battery-grade cobaltosic oxide is finally given；It is Chinese special
Sharp CN102249348B has invented a kind of preparation method of hexagonal piece cobaltosic oxide, by cobalt raw material, highly basic saturated solution with helping
Flux is well mixed, and sintered material is obtained after drying；After sintered material crushing, roasting, through natural cooling, sintered
Thing；The sinter is placed in 0.1~2.0M hydrochloric acid and soaked, the wet production of cobaltosic oxide hexagonal piece is obtained after scrubbed filtering
Product；After the wet product drying of the cobaltosic oxide hexagonal piece, product hexagonal piece cobaltosic oxide is produced.
Prior art can prepare the cobaltosic oxide of various different-shapes, but use substantial amounts of organic solvent, unfavorable
In large-scale production and pollution environment；Simultaneously four oxygen are also needed in terms of the electrode material as capacitor, catalysis aspect, absorption
Change three cobalts with higher specific surface area and abundant gap structure.Therefore, a kind of raw material is developed to be easy to get, be easy to scale chemical combination
Into, have great importance with high specific surface area, abundant gap structure cobaltosic oxide material.
The content of the invention
It is an object of the invention to provide a kind of purposes of porous cobaltosic oxide, porous four oxidation three disclosed by the invention
Cobalt structure novel and unique, with high specific surface area, abundant gap structure, method is simple and safe, be easy to industrialized production, mould
Plate removal technique is simpler, without using other chemical reagent, simplifies technique, has saved production cost, and product purity is high, can
It is used as high-performance super capacitor electrode material, vehicle maintenance service material and sorbing material.
To achieve the above object of the invention, the technical solution adopted by the present invention is：
Application of the porous cobaltosic oxide in capacitor electrode material is prepared.
Application of the porous cobaltosic oxide in vehicle maintenance service material is prepared.
Porous cobaltosic oxide disclosed by the invention is prepared by following methods：
（1）At room temperature, pollen is added in distilled water, stirring, ultrasonic disperse obtain mixture；By said mixture from
After heart separation, take solids to add in absolute ethyl alcohol, centrifugal treating, the solid after drying centrifugation are carried out after stirring, ultrasonic disperse
Thing, obtains the pollen of surface removal of impurities processing；
（2）Take the pollen of surface removal of impurities processing to be added in distilled water, then add inorganic cobalt salt, stirring, ultrasonic vibration；
Then ethylenediamine is added, mechanical agitation obtains mixed liquor；The weight ratio of the pollen and inorganic cobalt salt of surface removal of impurities processing is
（80~5）∶1；
（3）Surfactant is added in aqueous slkali, step is added after stirring（2）Mixed liquor in, stirring；Then in 5
At~90 DEG C, hydrazine hydrate is added dropwise, stirs 0.5~24 hour；Then obtain solids through Magneto separate, solids through distillation washing,
After absolute ethyl alcohol is washed, drying obtains cobaltosic oxide precursor；By above-mentioned cobaltosic oxide precursor in roasting at 200~290 DEG C
Burn 1~8 hour, obtain cobaltosic oxide powder composite particles；By above-mentioned cobaltosic oxide powder composite particles in 300~500
It is calcined 2~6 hours at DEG C, obtains porous cobaltosic oxide.
In the present invention, pollen is porous rape pollen；Rape is in China's large area plantation, and it can not only turn into beautiful
Landscape, yearning, vegetable seed oil expression also can be the dining table flavour enhancing of people, and rape pollen is even more to be easy to get, for the method for the present invention,
The preparation cost of porous cobaltosic oxide can be significantly reduced, the cost of end product is advantageously reduced, enterprise is not only contributed to
Industry is produced, more favourable to consumer.
In above-mentioned technical proposal, the inorganic cobalt salt is cobalt acetate, acetate hydrate cobalt, cobalt chloride, hydrated cobalt chloride, nitric acid
One or more in cobalt, nitric hydrate cobalt, cobaltous sulfate, cobalt sulfate hydrate.
In above-mentioned technical proposal, step（1）In, the ultrasonic disperse time is 5~30 minutes；The matter of pollen and distilled water
Amount is than being 1:（4~100）, the mass ratio of solids and absolute ethyl alcohol is 1:（4~100）.In order to preferably remove pollen surface
Impurity, Ethanol Treatment 3~6 times can be used, then the drying centrifugation thing under the conditions of 30~60 DEG C.
In above-mentioned technical proposal, step（2）In, pollen and the distilled water mass ratio of surface removal of impurities processing are 1:（5~20）；
Add after inorganic cobalt salt, stirring 10~120 minutes, ultrasonic vibration 2~5 minutes；Then ethylenediamine, mechanical agitation 10~30 are added
Minute obtains mixed liquor.
In above-mentioned technical proposal, step（3）In, surfactant is added in aqueous slkali, stirring is added after 5~10 minutes
Step（2）Mixed liquor in, stir 5~60 minutes.
In above-mentioned technical proposal, step（3）In, in order to obtain cleaner cobaltosic oxide precursor, solids is through steaming
Distilled water is washed, absolute ethyl alcohol is washed 3~5 times；Then dried under the conditions of 40~60 DEG C.
In above-mentioned technical proposal, step（2）In, the mol ratio of the ethylenediamine and inorganic cobalt salt is 1:（1~4）.
In above-mentioned technical proposal, step（3）In, the consumption of the surfactant is the 3%~20% of pollen quality；It is described
Aqueous slkali is sodium hydrate aqueous solution or potassium hydroxide aqueous solution；In the aqueous slkali, the mole of alkali is rubbed with inorganic cobalt salt
You are at amount ratio（40~90）∶1；The mole of the hydrazine hydrate and the mole ratio of inorganic cobalt salt are（300~550）∶1；Surface
Activating agent is PVP, cetyl trimethylammonium bromide or polyethylene glycol.
In above-mentioned technical proposal, kinds of surfactants is ionic surfactant PVP, hexadecane
Base trimethylammonium bromide, or nonionic surface active agent polyethylene glycol.
In above-mentioned technical proposal, obtained product is Porous hollow ball-type, and specific surface area is higher, hole relatively enriches, therefore
The porous cobaltosic oxide that the present invention is preferably prepared according to the above method, porous cobaltosic oxide is elliposoidal, and particle diameter is 6
~10 μm, the m of specific surface area 91~1202/ g, surface mesh size is 200~600 nm.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art:
（1）Present invention firstly discloses being template using pure biological pollen, with features such as green, natural, wide material sources,
Template removal technique is simpler, without using other chemical reagent, simplifies technique, has saved production cost, and product purity is high；
Obtained product is Porous hollow ball-type, and specific surface area is higher, hole relatively enriches, with unexpected property.
（2）Porous cobaltosic oxide disclosed by the invention is Porous hollow spheroid shape, and specific surface area is higher, hole is richer
Richness, and pore size is adjustable, can be used as high-performance super capacitor electrode material, vehicle maintenance service material and sorbing material.
Brief description of the drawings
Fig. 1 is the EDX spectrograms of porous cobaltosic oxide in embodiment one；
Fig. 2 is the SEM spectrograms of porous cobaltosic oxide in embodiment one；
Fig. 3 is the SEM spectrograms of porous cobaltosic oxide in embodiment two；
Fig. 4 is the SEM spectrograms of porous cobaltosic oxide in embodiment three；
Fig. 5 is the SEM spectrograms of porous cobaltosic oxide in example IV.
Embodiment
With reference to embodiment, accompanying drawing, the invention will be further described：
Embodiment one
At room temperature, 5 g porous rape pollen is added in 50 mL distilled water, after 30 min of stirring, ultrasonic disperse
5~30min.After said mixture is centrifuged, 50 mL absolute ethyl alcohols are added, are repeated the above steps 3 times, fully to go
Except the impurity on its surface.Then, the product after centrifugation is put into 30 DEG C of baking oven and dried.At room temperature, take what 1 g had been pre-processed
Pollen is added in 10 mL distilled water, then adds ultrasonic vibration 3 min, Ran Houjia after 1 mmol cobalt acetates, 10 min of stirring
Enter 0.5 g ethylenediamines, the min of mechanical agitation 10 obtains mixed solution.At room temperature, 0.2 g PVP is added to 20 mL concentration
In the 2 mol/L NaOH aqueous solution, to stir 6 min.Solution after stirring is slowly dropped into mixed solution, mechanical agitation 10
min.The solution of above-mentioned mixing is heated to 65 DEG C, 20 mL hydrazine hydrate is then slowly dropped into, 1 h is stirred.Adopted after reaction completely
Product is separated with magnetic separation technique, is then respectively washed 3 times with distilled water and absolute ethyl alcohol.Then by product in 40 DEG C
Under the conditions of dry, you can obtain porous cobaltosic oxide predecessor.By obtained porous cobaltosic oxide predecessor at 200 DEG C
Roasting 1 hour, obtains cavernous carbon/cobaltosic oxide powder composite particles.Obtained composite particles are calcined at 300 DEG C
3 hours, obtain cavernous cobaltosic oxide powder.
Accompanying drawing 1 is the EDX spectrograms of above-mentioned porous cobaltosic oxide；It can be seen that having Co atoms, O former in product
Son and C atoms.Wherein, Co:O atomic ratio is about 3:4, with target product Co3O4Quite, as a result show, by calcining, product
For porous cobaltosic oxide.
Accompanying drawing 2 is the SEM spectrograms of above-mentioned porous cobaltosic oxide；It can be seen that product morphology is relatively regular, substantially
Maintain the pattern of original rape pollen.About 8 μm of the size of product.As a result show, can be prepared by simple method of the invention
Go out porous elliposoidal cobaltosic oxide.
Embodiment two
At room temperature, 10 g rape pollen is added in 80 mL, after 40 min of stirring, the min of ultrasonic disperse 20.Will be upper
State after mixture centrifugation, add 40 mL absolute ethyl alcohols, repeat the above steps 4 times, fully to remove the miscellaneous of its surface
Matter.Then, the product after centrifugation is put into 45 DEG C of baking oven and dried.At room temperature, the pollen for taking 2 g to pre-process is added to 30
In mL distilled water, the min of ultrasonic vibration 3 after 1.5 mmol hydrated cobalt chloride, 65 min of stirring is then added, then adds 4 g's
Ethylenediamine, the min of mechanical agitation 18 obtains mixed solution.At room temperature, 0.3 g polyethylene glycol 400 is added to the dense of 30 mL
Spend in the NaOH solution for 3 mol/L, stir 7 min.Solution after stirring is slowly added dropwise into mixed solution, mechanical agitation
40 min.The solution of above-mentioned mixing is heated to 70 DEG C, 25 mL hydrazine hydrate is then slowly dropped into, 8 h are stirred.Reaction is complete
Product is separated using magnetic separation technique afterwards, is then respectively washed 3 times with distilled water and absolute ethyl alcohol.Then by product in
Dried under the conditions of 45 DEG C, you can obtain porous cobaltosic oxide predecessor.Porous cobaltosic oxide predecessor is roasted at 260 DEG C
Burn 2 hours, obtain cavernous carbon/cobaltosic oxide powder composite particles.Composite particles are calcined 4 hours at 450 DEG C, are obtained
Cavernous cobaltosic oxide powder.
Accompanying drawing 3 is the SEM spectrograms of above-mentioned porous cobaltosic oxide；It can be seen that product morphology is relatively regular, substantially
Maintain the pattern of original rape pollen.About 10 μm of the size of product.As a result show, can be made by simple method of the invention
It is standby go out porous elliposoidal cobaltosic oxide.
Embodiment three
At room temperature, 15 g rape pollen is added in 80 mL distilled water, after 45 min of stirring, ultrasonic disperse 25
min.After said mixture is centrifuged, 100 mL absolute ethyl alcohols are added, are repeated the above steps 5 times, to fully removal
The impurity on its surface.Then, the product after centrifugation is put into 60 DEG C of baking oven and dried.At room temperature, take what 10 g had been pre-processed
Pollen is added in 65 mL distilled water, then adds ultrasonic vibration 5min after 2 mmol cobalt sulfate hydrates, 25 min of stirring, so
After add 4 g ethylenediamines, the min of mechanical agitation 15 obtains mixed solution.At room temperature, 0.5 g PVP is added to the dense of 40 mL
Spend in the NaOH solution for 3 mol/L, stir 7 min.Solution after stirring is slowly dropped into mixed solution, mechanical agitation 15
min.Above-mentioned mixed solution is heated to 75 DEG C, 35 mL hydrazine hydrate is then slowly dropped into, 2 h are stirred.Used after reaction completely
Magnetic separation technique is separated product, is then respectively washed 4 times with distilled water and absolute ethyl alcohol.Then by product in 45 DEG C of bars
Dried under part, you can obtain porous cobaltosic oxide predecessor；It is calcined 2 hours at 270 DEG C, obtains the oxygen of cavernous carbon/tetra-
Change three cobalt powder bluk recombination particles, composite particles are calcined 4 hours at 500 DEG C, obtain cavernous cobaltosic oxide powder.
Accompanying drawing 4 is the SEM spectrograms of above-mentioned porous cobaltosic oxide；It can be seen that product morphology is relatively regular, substantially
Maintain the pattern of original rape pollen.There is a small amount of particle that obviously hollow structure is presented, show, product is a kind of porous
Hollow-core construction cobaltosic oxide.About 8 μm of the size of product.As a result show, can be prepared by simple method of the invention many
The elliposoidal cobaltosic oxide in hole.
Example IV
At room temperature, 20 g rape pollen is added in 200 mL distilled water, after 60 min of stirring, ultrasonic disperse 30
min.After said mixture is centrifuged, 250 mL absolute ethyl alcohols are added, are repeated the above steps 3 times, to fully removal
The impurity on its surface.Then, the product after centrifugation is put into 55 DEG C of baking oven and dried.At room temperature, take what 10 g had been pre-processed
Pollen is added in 65 mL distilled water, then adds ultrasonic vibration 4min, Ran Houjia after 3 mmol cobalt nitrates, 80 min of stirring
Enter 5 g ethylenediamines, the min of mechanical agitation 20 obtains mixed solution.At room temperature, 0.6 g CTAB is added to 60 mL concentration
In KOH solution for 4 mol/L, 10 min are stirred.Solution after stirring is slowly dropped into mixed solution, mechanical agitation 55
min.The solution of above-mentioned mixing is heated to 80 DEG C, 40 mL hydrazine hydrate is then slowly dropped into, 18 h are stirred.After reaction completely
Product is separated using magnetic separation technique, is then respectively washed 5 times with distilled water and absolute ethyl alcohol.Then by product in 60
Under the conditions of DEG C dry, you can obtain porous cobaltosic oxide predecessor, at 270 DEG C be calcined 5 hours, obtain cavernous carbon/
Cobaltosic oxide powder composite particles；Composite particles are calcined 6 hours at 450 DEG C, obtain cavernous cobaltosic oxide powder.
Accompanying drawing 5 is the SEM spectrograms of above-mentioned porous cobaltosic oxide；It can be seen that product morphology is relatively regular, substantially
Maintain the pattern of original rape pollen.There is a small amount of particle that obviously hollow structure is presented, show, product is a kind of porous
Hollow-core construction cobaltosic oxide.About 7 μm of the size of product.As a result show, can be prepared by simple method of the invention many
The elliposoidal cobaltosic oxide in hole.
The sign of above-mentioned porous cobaltosic oxide is shown in Table 1, in illustrating that the porous cobaltosic oxide of the invention prepared is porous
Empty spheroid shape, specific surface area is higher, hole relatively enriches, and pore size is adjustable, can be used as high-performance super capacitor electrode material
Material, vehicle maintenance service material and sorbing material.
Porous cobaltosic oxide performance parameter in the embodiment of table 1
| Embodiment one | Embodiment two | Embodiment three | Example IV | |
| Specific surface area/m2.g-1 | 118 | 112 | 101 | 92 |
| Mesh size/nm | 220 | 340 | 560 | 580 |
| Particle diameter/μm | 6 | 10 | 8 | 7 |
Embodiment five
Vehicle exhaust test experiments method：When the porous cobaltosic oxide material of the present invention is used as into vehicle maintenance service,
A certain amount of porous cobaltosic oxide is taken, the reacting gas of simulation is passed through, constituted（Percent by volume）For 1% CO, 19% O2, its
It is remaining to use N2Gas is balanced, and the flow velocity of reacting gas is 100 ml/min, the gas composition gas chromatographic detection of reactor outlet.Root
According to gas chromatographic detection result, the CO conversion ratios under different temperatures can be obtained, i.e., the porous many vehicle exhausts of cobaltosic oxide
Absorption degradation rate, is shown in Table 2.It can be seen that the porous cobaltosic oxide specific surface area of the present invention is higher, hole relatively enriches, can be effective
Handle vehicle exhaust.
Conversion ratio of the porous cobaltosic oxide to carbon monoxide under the different temperatures of table 2
| Embodiment one | Embodiment two | Embodiment three | Example IV | |
| 350℃ | 90.7% | 87.6% | 70.6% | 64.2% |
| 400℃ | 94.2% | 92.1% | 88.1% | 86.2% |
| 500℃ | 99.8% | 98.2% | 88.4% | 87.2% |
| 550℃ | 99.9% | 99.9% | 99.8% | 99.9% |
Embodiment six
The experimental method of capacitance electrode：Porous cobaltosic oxide material be used for capacitor electrode material when with higher ratio
Capacity, specific experiment method is by porous cobaltosic oxide and acetylene black, polytetrafluoroethylene (PTFE)（Mass ratio 6: 3: 1）It is uniform after mixing
1cm is prepared into after coating nickel screen, air drying2Electrode, then by the application of electrode into ultracapacitor, is once increasing electricity
Its specific capacity is tested under the conditions of current density, 3 are shown in Table.It can be seen that the porous cobaltosic oxide specific surface area of the present invention is higher, hole
Gap is relatively enriched, and is conducive to the entrance and migration of electrolyte ion, electrode material prepared therefrom, which is applied to ultracapacitor, to be had
Higher specific capacity.
Supercapacitor specific capacity under the different current densities of table 3
| Embodiment one | Embodiment two | Embodiment three | Example IV | |
| 0.5 A/g | 781 F/g | 721 F/g | 706F/g | 630 F/g |
| 5 A/g | 421 F/g | 412 F/g | 395 F/g | 350 F/g |
| 8 A/g | 380 F/g | 360 F/g | 326 F/g | 319 F/g |
Claims (5)
1. application of the porous cobaltosic oxide in vehicle maintenance service material is prepared；
The porous cobaltosic oxide is prepared by following methods：
（1）At room temperature, pollen is added in distilled water, stirring, ultrasonic disperse obtain mixture；By said mixture centrifugation point
From rear, take solids to add in absolute ethyl alcohol, centrifugal treating is carried out after stirring, ultrasonic disperse, the solids after drying centrifugation is obtained
The pollen handled to surface removal of impurities；The pollen is porous rape pollen；The ultrasonic disperse time is 5~30 minutes；Pollen
Mass ratio with distilled water is 1:（4~100）, the mass ratio of solids and absolute ethyl alcohol is 1:（4~100）；
（2）Take the pollen of surface removal of impurities processing to be added in distilled water, then add inorganic cobalt salt, stirring, ultrasonic vibration；Then
Ethylenediamine is added, mechanical agitation obtains mixed liquor；The inorganic cobalt salt is cobalt acetate, acetate hydrate cobalt, cobalt chloride, chloride hydrate
One or more in cobalt, cobalt nitrate, nitric hydrate cobalt, cobaltous sulfate, cobalt sulfate hydrate；The pollen of surface removal of impurities processing with
The weight ratio of inorganic cobalt salt is（80~5）∶1；
（3）Surfactant is added in aqueous slkali, step is added after stirring（2）Mixed liquor in, stirring；Then in 5~90
At DEG C, hydrazine hydrate is added dropwise, stirs 0.5~24 hour；Then solids is obtained through Magneto separate, solids is through distillation washing, anhydrous
After ethanol is washed, drying obtains cobaltosic oxide precursor；By above-mentioned cobaltosic oxide precursor at 200~290 DEG C roasting 1~
8 hours, obtain cobaltosic oxide powder composite particles；By above-mentioned cobaltosic oxide powder composite particles in roasting at 300~500 DEG C
Burn 2~6 hours, obtain porous cobaltosic oxide；
The porous cobaltosic oxide is elliposoidal, and particle diameter is 6~10 μm, 91~120m of specific surface area2/ g, surface mesh size
For 200~600nm.
2. application of the porous cobaltosic oxide in capacitor electrode material is prepared；
The porous cobaltosic oxide is prepared by following methods：
（1）At room temperature, pollen is added in distilled water, stirring, ultrasonic disperse obtain mixture；By said mixture centrifugation point
From rear, take solids to add in absolute ethyl alcohol, centrifugal treating is carried out after stirring, ultrasonic disperse, the solids after drying centrifugation is obtained
The pollen handled to surface removal of impurities；The pollen is porous rape pollen；The ultrasonic disperse time is 5~30 minutes；Pollen
Mass ratio with distilled water is 1:（4~100）, the mass ratio of solids and absolute ethyl alcohol is 1:（4~100）；
（2）Take the pollen of surface removal of impurities processing to be added in distilled water, then add inorganic cobalt salt, stirring, ultrasonic vibration；Then
Ethylenediamine is added, mechanical agitation obtains mixed liquor；The inorganic cobalt salt is cobalt acetate, acetate hydrate cobalt, cobalt chloride, chloride hydrate
One or more in cobalt, cobalt nitrate, nitric hydrate cobalt, cobaltous sulfate, cobalt sulfate hydrate；The pollen of surface removal of impurities processing with
The weight ratio of inorganic cobalt salt is（80~5）∶1；
（3）Surfactant is added in aqueous slkali, step is added after stirring（2）Mixed liquor in, stirring；Then in 5~90
At DEG C, hydrazine hydrate is added dropwise, stirs 0.5~24 hour；Then solids is obtained through Magneto separate, solids is through distillation washing, anhydrous
After ethanol is washed, drying obtains cobaltosic oxide precursor；By above-mentioned cobaltosic oxide precursor at 200~290 DEG C roasting 1~
8 hours, obtain cobaltosic oxide powder composite particles；By above-mentioned cobaltosic oxide powder composite particles in roasting at 300~500 DEG C
Burn 2~6 hours, obtain porous cobaltosic oxide；
The porous cobaltosic oxide is elliposoidal, and particle diameter is 6~10 μm, 91~120m of specific surface area2/ g, surface mesh size
For 200~600nm.
3. applied according to claims 1 or 2, it is characterised in that：Step（2）In, the pollen of surface removal of impurities processing and steaming
Distilled water mass ratio is 1:（5~20）；Add after inorganic cobalt salt, stirring 10~120 minutes, ultrasonic vibration 2~5 minutes；Then plus
Enter ethylenediamine, mechanical agitation obtains mixed liquor in 10~30 minutes；The mol ratio of the ethylenediamine and inorganic cobalt salt is 1:（1~4）.
4. applied according to claims 1 or 2, it is characterised in that：Step（3）In, surfactant is added into aqueous slkali
In, stirring adds step after 5~10 minutes（2）Mixed liquor in, stir 5~60 minutes；Solids is through distillation washing, anhydrous second
Alcohol is washed 3~5 times；Then dried under the conditions of 40~60 DEG C.
5. applied according to claims 1 or 2, it is characterised in that：Step（3）In, the consumption of the surfactant is
The 3%~20% of pollen quality；The aqueous slkali is sodium hydrate aqueous solution or potassium hydroxide aqueous solution；In the aqueous slkali, alkali
Mole and the mole ratio of inorganic cobalt salt be（40~90）∶1；The mole of the hydrazine hydrate and the mole of inorganic cobalt salt
Than for（300~550）∶1；Surfactant is polyvinylpyrrolidone, cetyl trimethylammonium bromide or polyethylene glycol.
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| CN106335930B (en) * | 2016-08-16 | 2018-09-18 | 安徽师范大学 | Porous spherical cobaltosic oxide electrode material and its preparation method and application |
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| CN100391828C (en) * | 2006-07-07 | 2008-06-04 | 南开大学 | General method for preparing spherical porous metal oxide |
| CN103011306B (en) * | 2013-01-04 | 2014-12-10 | 南京工业大学 | Method for preparing nanometer-level cube-like cobaltosic oxide |
| CN103274482A (en) * | 2013-06-17 | 2013-09-04 | 中国科学院上海硅酸盐研究所 | Mesoporous Co3O4 material with high specific surface area and crystallization hole wall, as well as preparation method and application thereof |
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