CN107742584A - One seed nucleus nucleocapsid trielement composite material Co3O4/PANI/MnO2Preparation method and use - Google Patents

One seed nucleus nucleocapsid trielement composite material Co3O4/PANI/MnO2Preparation method and use Download PDF

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CN107742584A
CN107742584A CN201710742196.5A CN201710742196A CN107742584A CN 107742584 A CN107742584 A CN 107742584A CN 201710742196 A CN201710742196 A CN 201710742196A CN 107742584 A CN107742584 A CN 107742584A
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pani
mno
core
composite material
preparation
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王莹莹
王畅
王义军
郝臣
王晓红
高海文
周赛赛
杨滢璐
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Jiangsu University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention belongs to composite synthesis technical field, it is related to Co3O4/PANI/MnO2The preparation method of composite, more particularly to a seed nucleus nucleocapsid trielement composite material Co3O4/PANI/MnO2Preparation method.The present invention has selected relatively low cost, aboundresources and free of contamination conventional material Co3O4And MnO2, it is compound with the preferable PANI of electric conductivity, successfully devise a seed nucleus nucleocapsid heterojunction structure.Using nickel foam as collector, by the Co of hydro-thermal method preparation3O4Nano-wire array provides small portion electric capacity as kernel, then by Co3O4As skeleton, with Co3O4Nickel foam surface electrochemistry deposit one layer of PANI film as outer core, store a part of electric charge and quickly transmitted for electronics and effective approach is provided, improve the electric conductivity of material, finally using manganese dioxide made from hydro-thermal method as shell, the capacitive property of material is further improved, so as to obtain a kind of ternary nano composite material Co that may be used as electrode of super capacitor of binder free3O4/PANI/MnO2。

Description

One seed nucleus-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Preparation method and Purposes
Technical field
The invention belongs to composite synthesis technical field, it is related to Co3O4/PANI/MnO2The preparation method of composite, More particularly to one seed nucleus-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Preparation method and use.
Background technology
With significantly improving for human living standard, the development of the consumer electronics industry is maked rapid progress, to ultracapacitor (SC) demand is increasing, the requirement more and more higher to its electrode material performance.SC electrode materials are no longer limited to single Material, possesses special construction and the good multi-element composite material of capacitive property has turned into the emphasis of research, has core shell hetero-junctions The characteristic of different materials in the nano composite material of structure, not only larger active surface area and shorter ion diffusion path, and And show potentially to act synergistically between each component.Therefore, the design of the core shell nano composite material with loose structure is closed The development of paired high performance electrode material has good application prospect.
Metal oxide such as Co3O4、MnO2, NiO, CuO etc. be all common SC electrode materials, they pass through redox Reaction storage electric charge.Wherein MnO2With nature content is high, cost is low, environmentally friendly and big theoretical specific capacitance value excellent Point, but because its load capacity is relatively low, specific capacitance value is not high, it is necessary to poly- with other metal ions or conduction in actual applications Compound polymerization improves its load capacity and electric conductivity.Co3O4Effective support material can be used as, as interior in core/shell structure Core, meets the needs of electrode material structural stability, but its electric conductivity is not also high.Polyaniline (PANI), as a kind of conductive poly- Compound, effective path can be not only provided for electronics fast transfer, and can accelerated between electric activity center and collector Kinetics.
At present, the research of ternary layering nanostructured is made using one-dimensional nano line as kernel, transition metal oxide more For shell, to improve kernel electric conductivity, one layer of conducting polymer is loaded again outside kernel mostly.
The content of the invention
The purpose of the present invention is using nickel foam as collector, by the Co of hydro-thermal method preparation3O4Nano-wire array as kernel, Then by Co3O4As skeleton, with Co3O4Nickel foam surface electrochemistry deposit one layer of PANI film as outer core, finally Using manganese dioxide made from hydro-thermal method as shell, so as to obtain a kind of ternary nano that may be used as SC electrodes of binder free Composite Co3O4/PANI/MnO2。
Technical scheme is as follows：
One seed nucleus-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Preparation, comprise the following steps：
Step 1, in proportion by cobalt nitrate hexahydrate, ammonium fluoride, urea and a certain amount of cetyl trimethylammonium bromide (CTAB) it is dissolved in deionized water, is configured to precursor solution；
Step 2, piece of foam nickel (1cm × 1cm) cleaned with hydrochloric acid, acetone and deionized water respectively in advance, then put Enter reactor, be immersed in the precursor solution obtained by step 1, heating response, after reaction terminates, the foam of product will have been loaded Nickel substrate distinguishes 1~10min of ultrasonic disperse in deionized water and ethanol, then cleans up, after being put into oven drying, by sample Product are placed in Muffle furnace and calcined, and Co is obtained in nickel foam3O4Nano wire；
Step 3, to be obtained in step 2 with Co3O4The nickel foam of nano wire is working electrode, and platinum electrode is as auxiliary Electrode, saturated calomel electrode is as reference electrode, in the deposition liquid of the aniline containing sulfuric acid and by pretreatment, constant potential electricity Polyaniline film is deposited, sedimentation potential 0.6V, after electro-deposition for a period of time, product is used into deionized water and alcohol flushing respectively, Oven drying is put into, Co is obtained in nickel foam3O4/PANI；
Step 4, by step 3 obtain with Co3O4The nickel foam of nano wire and polyaniline film is put into liquor potassic permanganate In, hydro-thermal reaction certain time, product is then distinguished into 1~10min of ultrasound in deionized water, ethanol, cleans up, is put into Oven drying, obtain composite Co3O4/PANI/MnO2。
In step 1, in precursor solution, cobalt nitrate hexahydrate, ammonium fluoride, urea, cetyl trimethylammonium bromide and go The amount ratio of ionized water is:0.31g：0.085g：0.3226g：0.05~0.4g：30mL.
In step 2, the concentration of hydrochloric acid and acetone is 1molL-1。
In step 2, in reactor, the temperature of heating response is 100~150 DEG C, and the time of reaction is 8~12h；Drying temperature Spend for 60 DEG C；In Muffle furnace, calcining heat is 300~500 DEG C, calcination time 3h；
In step 3, in described deposition liquid, the concentration of sulfuric acid is 0.25molL-1；The concentration of aniline is 0.1molL-1。
In step 3, the sedimentation time of electro-deposition is 2~8min；Drying temperature is 60 DEG C.
In step 4, the concentration of liquor potassic permanganate is 0.02molL-1；The volume of liquor potassic permanganate：The water of step 1 six The quality of cobalt nitrate is 25mL：0.31g.
In step 4, during the hydro-thermal reaction, reaction temperature is 100~150 DEG C, and the reaction time is 2~6h；Drying temperature For 60 DEG C.
The preprocess method of aniline used in the present invention is：A small amount of aniline monomer is poured into flask, is put into zeolite, magnetic Son, it is 130 DEG C to set oil bath pot temperature, builds decompressor, connects vavuum pump and be evaporated under reduced pressure, vacuum pump pressure Between 0.93MPa~0.95MPa, in still-process, prevent aniline from aoxidizing by adding a small amount of zinc powder, on 105 DEG C of left sides The right side has cut to steam, and removes front-end volatiles and obtains colorless oil aniline.
Ternary nano composite material Co prepared by the present invention3O4/PANI/MnO2For preparing ultracapacitor.
This experiment agents useful for same is all that analysis is pure, is commercially available.
Beneficial effects of the present invention are：
The present invention is by simple method, and using simple cost, design, which has synthesized one kind, has core-core-shell structure copolymer hetero-junctions The Co of structure3O4/PANI/MnO2, for the material of synthesis with distinct core-nucleocapsid structure, pattern is good, is suitable as super capacitor The electrode material of device, is easy to industrialized production.
Brief description of the drawings
Fig. 1 is scanning electron microscope (SEM) photograph, wherein (a-b) is MnO2Scanning electron microscope (SEM) photograph, (c-d) is Co3O4Scanning electron microscope (SEM) photograph, (e-f) it is Co3O4/ PANI scanning electron microscope (SEM) photograph, (g-h) are the scanning electron microscope (SEM) photographs of the sample of embodiment 2.
Fig. 2 is transmission electron microscope picture, wherein (a) is MnO2Transmission electron microscope picture, (b) be the sample of embodiment 2 transmission electricity Mirror figure.
Embodiment
With reference to specific implementation example, the present invention will be further described, so that those skilled in the art more fully understand The present invention, but the invention is not limited in following examples.
Embodiment 1
Accurately weigh 0.31g cobalt nitrate hexahydrates, 0.085g ammonium fluorides, 0.3226g urea and 0.05g cetyl trimethyls Ammonium bromide (CTAB) is dissolved in 30mL deionized waters, is configured to precursor solution, is subsequently poured into 50mL reactors；
Piece of foam nickel (1cm × 1cm) is used into 1molL respectively in advance-1Hydrochloric acid, acetone and deionized water cleaning, with After be put into reactor, be immersed in above-mentioned solution, reaction 8h of the reactor at 100 DEG C, the foam nickel base of product will have been loaded Ultrasonic disperse 1min is distinguished in deionized water and ethanol, then cleans up, after being put into 60 DEG C of oven drying, sample is put 300 DEG C of calcining 3h, obtain Co in nickel foam in Muffle furnace3O4Nano wire；
Then, to obtain with Co3O4The nickel foam of nano wire is working electrode, and platinum electrode is as auxiliary electrode, saturation Calomel electrode is containing 0.25molL as reference electrode-1Sulfuric acid and 0.1molL-1In the deposition liquid of aniline, constant potential Electro-deposition polyaniline film, sedimentation potential 0.6V, sedimentation time 2min, product is used into deionized water and alcohol flushing respectively, 60 DEG C drying, obtains Co in nickel foam3O4/PANI；
Then will obtain with Co3O4It is 0.02mol that the nickel foam of nano wire and polyaniline film, which is put into 25mL concentration, L-1Liquor potassic permanganate in, in 100 DEG C of hydro-thermal reaction 2h, product is then distinguished into ultrasonic 1min in deionized water, ethanol, Clean up, 60 DEG C of dryings, obtain composite Co3O4/PANI/MnO2。
Embodiment 2
Accurately weigh 0.31g cobalt nitrate hexahydrates, 0.085g ammonium fluorides, 0.3226g urea and 0.1g cetyl trimethyls Ammonium bromide (CTAB) is dissolved in 30mL deionized waters, is configured to precursor solution；It is subsequently poured into 50mL reactors；
Piece of foam nickel (1cm × 1cm) is used into 1molL respectively in advance-1Hydrochloric acid, acetone and deionized water cleaning, with After be put into reactor, be immersed in above-mentioned solution, reaction 10h of the reactor at 120 DEG C, the foam nickel base of product will have been loaded Ultrasonic disperse 1min is distinguished in deionized water and ethanol, then cleans up, after being put into 60 DEG C of oven drying, sample is put 350 DEG C of calcining 3h, obtain Co in nickel foam in Muffle furnace3O4Nano wire；
Then, to obtain with Co3O4The nickel foam of nano wire is working electrode, and platinum electrode is as auxiliary electrode, saturation Calomel electrode is containing 0.25molL as reference electrode-1Sulfuric acid and 0.1molL-1In the deposition liquid of aniline, constant potential Electro-deposition polyaniline film, sedimentation potential 0.6V, sedimentation time 4min, product is used into deionized water and alcohol flushing respectively, 60 DEG C drying, obtains Co in nickel foam3O4/PANI；
Then will obtain with Co3O4It is 0.02mol that the nickel foam of nano wire and polyaniline film, which is put into 25mL concentration, L-1Liquor potassic permanganate in, in 120 DEG C of hydro-thermal reaction 4h, product is then distinguished into ultrasonic 1min in deionized water, ethanol, Clean up, 60 DEG C of dryings, obtain composite Co3O4/PANI/MnO2。
In Fig. 1, the nanometer MnO that foam nickel skeleton is produced can be seen that according to a and c2And Co3O4Uniform fold, without it His impurity.It can be seen from b, nanometer MnO2In lamella flower ball-shaped structure, bouquet diameter about 100nm or so, from d as can be seen that Co3O4It is the smooth nanowire array structure in surface, average diameter 50nm-80nm, length has a few to tens of microns.By comparing b And d, the specific surface area of flower ball-shaped manganese dioxide is more slightly larger than oxidation cobalt nanowire, may infer that MnO2Chemical property compare Co3O4 It is better.After deposited PANI, e-f is such as schemed, nano-wire array average diameter becomes big, 100nm-120nm or so, in original Co3O4 There is layer of transparent shape material on the surface of nano wire skeleton, and PANI depositions are more., it is apparent that there is dioxy from g-h Change manganese nanometer bouquet to be coated on outside the nano wire that diameter becomes big, it was demonstrated that there is the Co of core-core-shell structure copolymer heterojunction structure3O4/PANI/MnO2 It is successfully prepared.
In Fig. 2, according to a it can be seen that the sheet bouquet structure of nano-manganese dioxide, bouquet diameter about 120nm.From b In it is observed that the kernel for having 80nm or so at the center of nano wire should be cobalt oxide skeleton, in the pitch black of kernel both sides Color part is probably the PANI outer cores of deposition, and only sedimentary is thicker, is manganese dioxide in the material of outermost edge stratiform Shell, it follows that consistent with scan image result by the information that images of transmissive electron microscope reflects, can prove with core-core- The Co of shell structure3O4/PANI/MnO2Success synthesizes.
Embodiment 3
Accurately weigh 0.31g cobalt nitrate hexahydrates, 0.085g ammonium fluorides, 0.3226g urea and 0.1g cetyl trimethyls Ammonium bromide (CTAB) is dissolved in 30mL deionized waters, is configured to precursor solution, is subsequently poured into 50mL reactors；
Piece of foam nickel (1cm × 1cm) is used into 1molL respectively in advance-1Hydrochloric acid, acetone and deionized water cleaning, with After be put into reactor, be immersed in above-mentioned solution, reaction 12h of the reactor at 150 DEG C, the foam nickel base of product will have been loaded Ultrasonic disperse 1min is distinguished in deionized water and ethanol, then cleans up, after being put into 60 DEG C of oven drying, sample is put 500 DEG C of calcining 3h, obtain Co in nickel foam in Muffle furnace3O4Nano wire；
Then, to obtain with Co3O4The nickel foam of nano wire is working electrode, and platinum electrode is as auxiliary electrode, saturation Calomel electrode is containing 0.25molL as reference electrode-1Sulfuric acid and 0.1molL-1In the deposition liquid of aniline, constant potential Electro-deposition polyaniline film, sedimentation potential 0.6V, sedimentation time 8min, product is used into deionized water and alcohol flushing respectively, 60 DEG C drying, obtains Co in nickel foam3O4/PANI；
Then will obtain with Co3O4It is 0.02mol that the nickel foam of nano wire and polyaniline film, which is put into 25mL concentration, L-1Liquor potassic permanganate in, in 120 DEG C of hydro-thermal reaction 4h, product is then distinguished into ultrasonic 1min in deionized water, ethanol, Clean up, 60 DEG C of dryings, obtain composite Co3O4/PANI/MnO2。
Embodiment 4
Accurately weigh 0.31g cobalt nitrate hexahydrates, 0.085g ammonium fluorides, 0.3226g urea and 0.4g cetyl trimethyls Ammonium bromide (CTAB) is dissolved in 30mL deionized waters, is configured to precursor solution, is subsequently poured into 50mL reactors；
Piece of foam nickel (1cm × 1cm) is used into 1molL respectively in advance-1Hydrochloric acid, acetone and deionized water cleaning, with After be put into reactor, be immersed in above-mentioned solution, reaction 8h of the reactor at 120 DEG C, the foam nickel base of product will have been loaded Ultrasonic disperse 1min is distinguished in deionized water and ethanol, then cleans up, after being put into 60 DEG C of oven drying, sample is put 350 DEG C of calcining 3h, obtain Co in nickel foam in Muffle furnace3O4Nano wire；
Then, to obtain with Co3O4The nickel foam of nano wire is working electrode, and platinum electrode is as auxiliary electrode, saturation Calomel electrode is containing 0.25molL as reference electrode-1Sulfuric acid and 0.1molL-1In the deposition liquid of aniline, constant potential Electro-deposition polyaniline film, sedimentation potential 0.6V, sedimentation time 2min, product is used into deionized water and alcohol flushing respectively, 60 DEG C drying, obtains Co in nickel foam3O4/PANI；
Then will obtain with Co3O4It is 0.02mol that the nickel foam of nano wire and polyaniline film, which is put into 25mL concentration, L-1Liquor potassic permanganate in, in 150 DEG C of hydro-thermal reaction 2h, product is then distinguished into ultrasonic 1min in deionized water, ethanol, Clean up, 60 DEG C of dryings, obtain composite Co3O4/PANI/MnO2。
Embodiment 5
Accurately weigh 0.31g cobalt nitrate hexahydrates, 0.085g ammonium fluorides, 0.3226g urea and 0.05g cetyl trimethyls Ammonium bromide (CTAB) is dissolved in 30mL deionized waters, is configured to precursor solution, is subsequently poured into 50mL reactors；
Piece of foam nickel (1cm × 1cm) is used into 1molL respectively in advance-1Hydrochloric acid, acetone and deionized water cleaning, with After be put into reactor, be immersed in above-mentioned solution, reaction 10h of the reactor at 120 DEG C, the foam nickel base of product will have been loaded Ultrasonic disperse 1min is distinguished in deionized water and ethanol, then cleans up, after being put into 60 DEG C of oven drying, sample is put 300 DEG C of calcining 3h, obtain Co in nickel foam in Muffle furnace3O4Nano wire；
Then, to obtain with Co3O4The nickel foam of nano wire is working electrode, and platinum electrode is as auxiliary electrode, saturation Calomel electrode is containing 0.25molL as reference electrode-1Sulfuric acid and 0.1molL-1In the deposition liquid of aniline, constant potential Electro-deposition polyaniline film, sedimentation potential 0.6V, sedimentation time 4min, product is used into deionized water and alcohol flushing respectively, 60 DEG C drying, obtains Co in nickel foam3O4/PANI；
Then will obtain with Co3O4It is 0.02mol that the nickel foam of nano wire and polyaniline film, which is put into 25mL concentration, L-1Liquor potassic permanganate in, in 120 DEG C of hydro-thermal reaction 6h, product is then distinguished into ultrasonic 1min in deionized water, ethanol, Clean up, 60 DEG C of dryings, obtain composite Co3O4/PANI/MnO2。
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair The equivalent structure or equivalent flow conversion that bright specification is made, or other related technical areas are directly or indirectly used in, Similarly it is included within the scope of the present invention.

Claims (9)

1. one seed nucleus-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Preparation method, it is characterised in that including following step Suddenly：
Step 1, in proportion by cobalt nitrate hexahydrate, ammonium fluoride, urea and a certain amount of cetyl trimethylammonium bromide (CTAB) It is dissolved in deionized water, is configured to precursor solution；
Step 2, piece of foam nickel cleaned with hydrochloric acid, acetone and deionized water respectively in advance, be subsequently placed into reactor, be immersed in In precursor solution obtained by step 1, heating response, after reaction terminates, the foam nickel base of product will be loaded in deionization 1~10min of ultrasonic disperse is distinguished in water and ethanol, then cleans up, after being put into oven drying, sample is placed in Muffle furnace Calcining, obtains Co in nickel foam3O4Nano wire；
Step 3, to be obtained in step 2 with Co3O4The nickel foam of nano wire is working electrode, platinum electrode as auxiliary electrode, Saturated calomel electrode is as reference electrode, in the deposition liquid of the aniline containing sulfuric acid and by pretreatment, constant potential electro-deposition Polyaniline film, sedimentation potential 0.6V, after electro-deposition for a period of time, product is used into deionized water and alcohol flushing respectively, is put into Oven drying, Co is obtained in nickel foam3O4/PANI；
Step 4, by step 3 obtain with Co3O4The nickel foam of nano wire and polyaniline film is put into liquor potassic permanganate, Hydro-thermal reaction certain time, product is then distinguished into 1~10min of ultrasound in deionized water, ethanol, cleans up, is put into baking Case is dried, and obtains composite Co3O4/PANI/MnO2。
2. core according to claim 1-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Preparation method, its feature It is：In step 1, in precursor solution, cobalt nitrate hexahydrate, ammonium fluoride, urea, cetyl trimethylammonium bromide and deionization The amount ratio of water is:0.31g：0.085g：0.3226g：0.05~0.4g：30mL.
3. core according to claim 1-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Preparation method, its feature It is：In step 2, the concentration of hydrochloric acid and acetone is 1molL-1。
4. core according to claim 1-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Preparation method, its feature It is：In step 2, in reactor, the temperature of heating response is 100~150 DEG C, and the time of reaction is 8~12h；Drying temperature For 60 DEG C；In Muffle furnace, calcining heat is 300~500 DEG C, calcination time 3h.
5. core according to claim 1-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Preparation method, its feature It is：In step 3, in described deposition liquid, the concentration of sulfuric acid is 0.25molL-1；The concentration of aniline is 0.1molL-1。
6. core according to claim 1-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Preparation method, its feature It is：In step 3, the sedimentation time of electro-deposition is 2~8min；Drying temperature is 60 DEG C.
7. core according to claim 1-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Preparation method, its feature It is：In step 4, the concentration of liquor potassic permanganate is 0.02molL-1；The volume of liquor potassic permanganate：The water nitric acid of step 1 six The quality of cobalt is 25mL：0.31g.
8. core according to claim 1-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Preparation method, its feature It is：In step 4, during the hydro-thermal reaction, reaction temperature is 100~150 DEG C, and the reaction time is 2~6h；Drying temperature is 60 ℃。
9. by core made from claim 1~8 preparation method-core-shell structure copolymer trielement composite material Co3O4/PANI/MnO2Material For preparing the purposes of ultracapacitor.
CN201710742196.5A 2017-08-25 2017-08-25 One seed nucleus nucleocapsid trielement composite material Co3O4/PANI/MnO2Preparation method and use Pending CN107742584A (en)

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US20130295461A1 (en) * 2010-12-21 2013-11-07 Tohoku University Nanoporous ceramic composite metal
CN105896000A (en) * 2016-04-20 2016-08-24 浙江大学 Co3O4/CNT/MnO2 array electrode of core-shell structure as well as preparation method and application thereof
CN106475111A (en) * 2016-09-21 2017-03-08 浙江大学 A kind of Co3O4@MnO2Nucleocapsid structure porous nano column material and preparation method thereof
CN106941152A (en) * 2017-04-12 2017-07-11 哈尔滨理工大学 A kind of preparation method of cobaltosic oxide nano rod/polyaniline nucleocapsid array electrode

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CN111063550A (en) * 2019-12-23 2020-04-24 江苏大学 Preparation method and application of hollow core-shell Fe-Co-based sulfide @ nickel hydroxide nanotube array
CN112331845A (en) * 2020-09-21 2021-02-05 昆明理工大学 Preparation method of cobaltosic oxide nanowire array negative electrode material
CN112331845B (en) * 2020-09-21 2021-09-07 昆明理工大学 Preparation method of cobaltosic oxide nanowire array negative electrode material
CN113921810A (en) * 2021-10-11 2022-01-11 中国科学技术大学 Ultrahigh-capacity zinc-cobalt battery positive electrode and self-activation preparation method thereof

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