CN107452512A - A kind of preparation method of hollow cobalt acid nickel for electrode material for super capacitor - Google Patents
A kind of preparation method of hollow cobalt acid nickel for electrode material for super capacitor Download PDFInfo
- Publication number
- CN107452512A CN107452512A CN201710695235.0A CN201710695235A CN107452512A CN 107452512 A CN107452512 A CN 107452512A CN 201710695235 A CN201710695235 A CN 201710695235A CN 107452512 A CN107452512 A CN 107452512A
- Authority
- CN
- China
- Prior art keywords
- preparation
- cobalt acid
- acid nickel
- electrode material
- hollow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 discloses a kind of preparation method of the hollow cobalt acid nickel for electrode material for super capacitor, silica nanosphere, Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea are dispersed in water, then hydro-thermal reaction is carried out at 90~150 DEG C 24~72 hours, collect solid product, products therefrom washing is calcined 2~10 hours after drying at 250~450 DEG C, produces the hollow cobalt acid nickel for being used for electrode material for super capacitor.The preparation method of the present invention, technique is simple, easily operated, and reaction condition is gentle, and cost is cheap, is easy to large-scale production, and the hollow cobalt acid nickel being prepared has the advantages of appearance structure is good, specific surface area is big, electrochemical performance；Compared to prior art, there are conspicuousness progress and industrial applications to be worth.
Description
Technical field
The present invention relates to a kind of preparation method of electrode material for super capacitor, is to be related to one kind for super specifically
The preparation method of the hollow cobalt acid nickel of capacitor electrode material, belongs to new energy technical field of nano material.
Background technology
Ultracapacitor is a kind of novel energy storage apparatus developed in recent years, has high power density, fast fills
The excellent specific properties such as discharge rate, the service life of length and wide operating temperature., can to cleaning with the enhancing of people's environmental consciousness
Higher requirement is proposed by the supply problem of the energy, ultracapacitor also turns into study hotspot.Electrode material is super capacitor
The core of device technology development, electrode material for super capacitor mainly have three major types, i.e. porous carbon materials, conducting polymer and transition
Metal oxide, wherein, transition metal oxide due to high stability, high specific capacitance and excellent cyclic reversibility, because
This is considered as preferable electrode material.In addition, in transition metal oxide, due to nickel oxide (NiO), cobaltosic oxide
(Co3O4) etc. there is environment-friendly, low cost, the advantages that being readily synthesized, it is most important that they have very high theoretical than electricity
Hold, these advantages make nickel, cobalt/cobalt oxide turn into the ideal electrode material of practical application.
Compound transition metal oxide is the polynary complexity being combined by two or more transition metal oxide
Oxide.It has better property than unit oxide, such as electrochemical educational circles, optics circle, magnetics circle property, also have steady
The property features such as qualitative good, corrosion-resistant, high temperature resistant, high rigidity.Cobalt acid nickel (NiCo2O4) be inverse spinel structure AB2O4Type
Composite oxides, wherein nickel ion occupy octahedral interstices, and cobalt occupies the octahedral interstices of whole tetrahedron spaces and half,
Its electric conductivity and electro-chemical activity are far above single nickel oxide (NiO), cobaltosic oxide (Co3O4), Co be present3+/Co2+And
Ni3+/Ni2+Oxidation-reduction pair, while have that cost is cheap, advantages of environment protection, electrode of super capacitor material can be used as
Material, has huge application value.
Traditional cobalt acid nickel is typically the structure such as solid sphere, sheet, wire, bar-shaped, and this cobalt acid nickel for writing structure compares table
Area is smaller, energy density is smaller, seriously limits the extension of its application.Research finds, the electrode material of hollow-core construction
Specific surface area is larger, therefore, it is necessary to the cobalt acid nickel for the hollow-core construction that specific surface area is larger, energy density is larger is developed, with
Improve its chemical property.
Research shows that the oxide recombiner condenser electrode material performance difference that the method for different preparations obtains is larger,
Therefore the technology of preparing of further research cobalt acid nickel capacitor electrode material is needed.At present, existing document report prepares cobalt acid nickel
Method have：High temperature solid-state method, sol-gel process, mechanochemical synthesis, liquid chemical precipitation method etc., but such method system
Standby cobalt acid nickel particle skewness, poor dispersion, yields poorly, and the relatively complicated complexity of preparation method.
Two methods are mainly distinguished in the preparation of current hollow cobalt acid nickel, and one kind is template-free method, and one kind is template.
Cobalt salt and nickel salt are mainly dissolved in appropriate organic solvent by template-free method, add auxiliary agent, at a certain temperature
Hollow cobalt acid nickel is made in reaction, products therefrom after calcining.Such as：One is disclosed in Chinese patent CN201410273050.7
Nickel nitrate and cobalt nitrate are dissolved in absolute ethyl alcohol by the preparation method of the hollow cobalt acid nickel of kind, this method, add oleyl amine, then dynamic
It is heat-treated in state reactor in 150 DEG C of reactions, products therefrom washing drying after at 200~400 DEG C, hollow sea urchin shape cobalt is made
Sour nickel；A kind of preparation method of cobalt acid nickel mesoporous microsphere is disclosed in Chinese patent CN201410423301.5, this method is with cobalt
Salt and nickel salt are raw material, using the mixed solvent of isopropanol and water as reaction medium, are entered after adding urea in hydrothermal reaction kettle
Water-filling thermal response, products therefrom washing drying are heat-treated after at 200~300 DEG C, and being made hemispherical or segment shape has sky
The cobalt acid nickel mesoporous microsphere of core structure；It is porous that a kind of a large amount of preparation graduation are disclosed in Chinese patent CN201510828004.3
The method of cobalt acid nickel nano-hollow box, nickel nitrate and cobalt nitrate are dissolved in polyethylene glycol by this method, while add sodium acetate, anti-
Answer in kettle and be heat-treated, be made by porous nano after at 350~400 DEG C in 180~220 DEG C of reactions, products therefrom washing drying
Line is the cobalt acid nickel nano-hollow box that primitive assembles；A kind of cobalt acid nickel is disclosed in Chinese patent CN201610463723.4
The preparation method of nano-hollow ball, cobalt nitrate hexahydrate, six water nickel nitrates are dissolved in glycerine and isopropanol by this method, 120
Hydro-thermal reaction is carried out at~200 DEG C, products therefrom washing is dried after high-temperature calcination at 400~600 DEG C, and core shell structure is made
Cobalt acid nickel nano-hollow ball.The above method, although the cobalt acid nickel of hollow-core construction can be made, obtained hollow cobalt acid nickel point
Cloth is not uniform enough, and structure appearance also has the defects of certain, and in preparation process, all inevitably uses organic molten
Agent, environmental pollution is caused unavoidably, be unsuitable for large-scale production.
Template is mainly using microballoons such as silica, aluminum oxide as template, in the area load cobalt acid nickel of microballoon, then
Etching removes microballoon, final high temperature calcining, hollow cobalt acid nickel is made.Such as：Disclosed in Chinese patent CN201510157615.X
Microballoon is scattered in second by a kind of preparation method of hollow cobalt acid nickel, this method using silica or aluminum oxide micro-sphere as template
In the aqueous solution of alcohol and hydroxypropyl cellulose, cobalt nitrate hexahydrate and six water nickel nitrates and urea are then added, at 50~90 DEG C
Reaction, products therefrom are washed after being calcined 1~3 hour at 200~400 DEG C, obtain including silica or aluminum oxide micro-sphere
Cobalt acid nickel core-shell structure, then core shell structure is placed in NaOH solution react 12~36 hours (etching remove silica or
Aluminum oxide micro-sphere), hollow cobalt acid nickel is made after being calcined 0.5~1 hour at 200~400 DEG C in products therefrom washing；It is Chinese special
A kind of preparation method of cobalt acid nickel hollow ball is disclosed in sharp CN201611112566.9, it is small that this method first prepares cuprous oxide
Ball, then using cuprous oxide bead as template, cuprous oxide bead and poly- acetyl pyrrole alkanone are scattered in second alcohol and water, so
Add nickel chloride afterwards and cobalt chloride is reacted, reaction adds Na after terminating2S2O3(etching removes cuprous oxide bead), product
Washing drying is calcined after at 280~320 DEG C, and cobalt acid nickel core ball is made.The above method, compared to template-free method, although being made
It is hollow, distribution it is more uniform, structure appearance is preferable, but needed in preparation process using acid (such as：Hydrofluoric acid) or alkali (example
Such as：Sodium hydroxide, ammoniacal liquor, sodium thiosulfate, sodium carbonate etc.) perform etching to remove the nanoparticle as template, it is not only right
Environment pollutes, and preparation technology is complex, and operation is relatively complicated, is unfavorable for large-scale production.
The content of the invention
In view of the above-mentioned problems existing in the prior art, it is an object of the invention to provide a kind of electrochemical performance, technique
Simply, cost is cheap, be easy to large-scale production the hollow cobalt acid nickel for electrode material for super capacitor preparation method.
For achieving the above object, the technical solution adopted by the present invention is as follows：
The preparation method of a kind of hollow cobalt acid nickel for electrode material for super capacitor, by silica nanosphere, six
Nitric hydrate nickel, cabaltous nitrate hexahydrate and urea are dispersed in water, and it is small that hydro-thermal reaction 24~72 is then carried out at 90~150 DEG C
When, solid product is collected, products therefrom washing is calcined 2~10 hours after drying at 250~450 DEG C, is produced described for surpassing
The hollow cobalt acid nickel of level capacitor electrode material.
Preferably, the mol ratio of Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate is：1：(2~3).
As further preferred scheme, molar concentration of the Nickelous nitrate hexahydrate in reaction solution is 0.01~0.1mol/L.
As further preferred scheme, 1mmol Nickelous nitrate hexahydrates need 0.01~1g silica nanospheres, 1mmol
Nickelous nitrate hexahydrate needs 1~10g urea.
Preferably, the silica nanosphere usesMethod synthesis is made.
As further preferred scheme,The concrete operations of legal system prepared silicon dioxide nanosphere are as follows：
Tetraethyl orthosilicate is added dropwise into the mixed solution system of alcohol water and ammoniacal liquor, it is small that 1~36 is stirred at 40~80 DEG C
When, make tetraethyl orthosilicate complete hydrolysis, reaction terminates, and centrifuges, produces the silica nanosphere.
As still more preferably scheme, 1 milliliter of tetraethyl orthosilicate uses the mixing of 10~120 milliliters of alcohol water and ammoniacal liquor
Solution.
As still more preferably scheme, it is 1 by volume by alcoholic solvent (such as ethanol) and water that the alcohol water, which is,:1~
20:1 (with 2:1~15:1 is optimal) formed；It is 8 by volume by alcohol water and ammoniacal liquor that the mixed solution of the alcohol water and ammoniacal liquor, which is,:1
~40:1 (with 10:1~35:1 is optimal) formed.
Compared with prior art, the present invention has following conspicuousness beneficial effect：
The present invention is using silica nanosphere as template, and the washing of gained solid product need not after drying after hydro-thermal reaction terminates
Through over etching, dinectly bruning can obtain hollow cobalt acid nickel (being free of silica nanosphere), reduces environmental pollution, reduces
Operating procedure, energy consumption is saved, improved yield, reduced production cost, beneficial to large-scale production；Especially, experiment shows：
The hollow cobalt acid nickel prepared by the inventive method, preferable with appearance structure, specific surface area is big, and electrochemical performance etc. is excellent
Point, there are preferable use value and application prospect on electrode material for super capacitor.
Brief description of the drawings
Fig. 1 is the scanning electron microscopic picture of hollow cobalt acid nickel prepared by embodiment 1；
Fig. 2 is the transmission electron microscope picture of hollow cobalt acid nickel prepared by embodiment 1.
Fig. 3 is the specific capacitance picture of hollow cobalt acid nickel prepared by embodiment 1.
Embodiment
Technical solution of the present invention is described in further detail and completely with reference to specific embodiment and comparative example.
Embodiment 1
First, useThe synthetically prepared silica nanosphere of method
The ammoniacal liquor stirring that 50mL absolute ethyl alcohols, 5mL water and 5mL concentration are 32wt% is allowed to well mixed, then stirred
Mix down and 2mL TEOS (tetraethyl orthosilicate) are added dropwise, stirred 20 hours at 60 times, terminate reaction, centrifuge, produce dioxy
SiClx nanosphere.
2nd, hollow cobalt acid nickel is prepared
By 0.1g silica nanospheres, 1mmol Nickelous nitrate hexahydrates, 2mmol cabaltous nitrate hexahydrates and 1.2g urea point
Dissipating in 50mL water, stirring is allowed to well mixed, hydro-thermal reaction is then carried out at 120 DEG C 48 hours, terminates reaction, separates,
Solid product is collected, the product of collection is washed with water and ethanol respectively, is dried, is then calcined 5 hours, produce at 300 DEG C
The hollow cobalt acid nickel for electrode material for super capacitor.
Embodiment 2
First, useThe synthetically prepared silica nanosphere of method
The ammoniacal liquor stirring that 50mL absolute ethyl alcohols, 5mL water and 5mL concentration are 32wt% is allowed to well mixed, then stirred
Mix down and 0.5mL TEOS (tetraethyl orthosilicate) are added dropwise, stirred 12 hours at 60 times, terminate reaction, centrifuge, produce two
Monox nanometer ball.
2nd, hollow cobalt acid nickel is prepared
By 0.5g silica nanospheres, 1mmol Nickelous nitrate hexahydrates, 2.5mmol cabaltous nitrate hexahydrates and 5g urea point
Dissipate in 50mL water, stirring is allowed to well mixed, hydro-thermal reaction is then carried out at 90 DEG C 72 hours, terminates reaction, separates, receives
Collect solid product, the product of collection wash with water and ethanol respectively, drying, then calcine 10 hours at 250 DEG C, produce described in
Hollow cobalt acid nickel for electrode material for super capacitor.
Embodiment 3
First, useThe synthetically prepared silica nanosphere of method
The ammoniacal liquor stirring that 50mL absolute ethyl alcohols, 5mL water and 5mL concentration are 32wt% is allowed to well mixed, then stirred
Mix down and 5mL TEOS (tetraethyl orthosilicate) are added dropwise, stirred 24 hours at 60 times, terminate reaction, centrifuge, produce dioxy
SiClx nanosphere.
2nd, hollow cobalt acid nickel is prepared
1g silica nanospheres, 1mmol Nickelous nitrate hexahydrates, 3mmol cabaltous nitrate hexahydrates and 10g urea are scattered in
In 50mL water, stirring is allowed to well mixed, hydro-thermal reaction is then carried out at 150 DEG C 24 hours, terminates reaction, separates, collects
Solid product, the product of collection is washed with water and ethanol respectively, dried, then calcined 2 hours at 450 DEG C, produce the use
In the hollow cobalt acid nickel of electrode material for super capacitor.
Comparative example
1mmol Nickelous nitrate hexahydrates, 2mmol cabaltous nitrate hexahydrates and 1.2g urea are scattered in 50mL water, stirring makes
It is well mixed, hydro-thermal reaction is then carried out at 120 DEG C 48 hours, terminate reaction, separation, collect solid product, to collecting
Product washed respectively with water and ethanol, dry, then calcine 5 hours at 300 DEG C, produce contrast cobalt acid nickel.
Below by taking embodiment 1 as an example, the present invention is further described with reference to accompanying drawing：
Fig. 1 is the scanning electron microscopic picture of hollow cobalt acid nickel prepared by embodiment 1；Fig. 2 is hollow cobalt acid prepared by embodiment 1
The transmission electron microscope picture of nickel；It is visible with reference to Fig. 1 and Fig. 2, use the inventive method can obtained cobalt acid nickel for hollow-core construction, and
Size is homogeneous, particle diameter distribution is uniform, overall appearance structure is good, has high porosity, is advantageous to the infiltration of electrolyte.
Fig. 3 is the specific capacitance picture of hollow cobalt acid nickel prepared by embodiment 1 and contrast cobalt acid nickel prepared by comparative example；Figure
In, square to represent the hollow cobalt acid nickel prepared using preparation method of the present invention, circle is represented in comparative example using tradition without mould
The contrast cobalt acid nickel that plate method is prepared, as seen from Figure 3, the hollow cobalt acid nickel prepared using preparation method of the present invention is compared to biography
The contrast cobalt acid nickel that system template-free method is prepared, has higher specific capacitance and capacity retention, therefore, has preferably electrification
Performance is learned, is particularly suited for electrode material for super capacitor.
In addition, after tested, hollow cobalt acid nickel prepared by the present invention, its specific surface area can reach 166.1m2/ g, specific capacitance
1229F/g can be reached under 1A/g current densities, there is excellent chemical property.
In summary, hydro-thermal reaction of the present invention terminates directly to be calcined products therefrom and can obtain being free of silica
The hollow cobalt acid nickel of nanosphere, compared to traditional template, silica nanosphere is entered using etching reagent without extra
Row etching, you can obtain described hollow cobalt acid nickel, preparation technology has that technique is simple, cost is cheap, reaction condition is gentle, produces
Rate height, favorable reproducibility, it is pollution-free, be easy to the advantages that scale；Especially, compared to traditional template-free method, it is prepared
Hollow cobalt acid nickel appearance structure is good, and specific surface area is big, has excellent chemical property, can be used as electrode material for super capacitor
Use；Compared to prior art, there are conspicuousness progress and industrial applications to be worth.
Finally need it is pointed out here that be：It the above is only the part preferred embodiment of the present invention, it is impossible to be interpreted as to this hair
The limitation of bright protection domain, those skilled in the art according to the present invention the above make some it is nonessential improvement and
Adjustment belongs to protection scope of the present invention.
Claims (6)
- A kind of 1. preparation method of hollow cobalt acid nickel for electrode material for super capacitor, it is characterised in that：By silica Nanosphere, Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea are dispersed in water, and it is anti-that hydro-thermal is then carried out at 90~150 DEG C Answer 24~72 hours, collect solid product, products therefrom washing is calcined 2~10 hours at 250~450 DEG C after drying, produced The hollow cobalt acid nickel for electrode material for super capacitor.
- 2. preparation method according to claim 1, it is characterised in that：Mole of Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate Than for：1：(2~3).
- 3. preparation method according to claim 2, it is characterised in that：Molar concentration of the Nickelous nitrate hexahydrate in reaction solution For 0.01~0.1mol/L.
- 4. preparation method according to claim 2, it is characterised in that：1mmol Nickelous nitrate hexahydrates need 0.01~1g bis- Monox nanometer ball, 1mmol Nickelous nitrate hexahydrates need 1~10g urea.
- 5. preparation method according to claim 1, it is characterised in that：The silica nanosphere usesMethod is closed Into be made.
- 6. preparation method according to claim 5, it is characterised in that：Legal system prepared silicon dioxide nanosphere it is specific Operation is as follows：Tetraethyl orthosilicate is added dropwise into the mixed solution system of alcohol water and ammoniacal liquor, stirs 1~36 hour, makes at 40~80 DEG C Tetraethyl orthosilicate complete hydrolysis, reaction terminate, and centrifuge, produce the silica nanosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710695235.0A CN107452512A (en) | 2017-08-15 | 2017-08-15 | A kind of preparation method of hollow cobalt acid nickel for electrode material for super capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710695235.0A CN107452512A (en) | 2017-08-15 | 2017-08-15 | A kind of preparation method of hollow cobalt acid nickel for electrode material for super capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107452512A true CN107452512A (en) | 2017-12-08 |
Family
ID=60491140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710695235.0A Pending CN107452512A (en) | 2017-08-15 | 2017-08-15 | A kind of preparation method of hollow cobalt acid nickel for electrode material for super capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107452512A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655120A (en) * | 2019-11-13 | 2020-01-07 | 东北电力大学 | Preparation method of mesoporous spherical nickel cobaltate nano material |
| CN111908522A (en) * | 2020-09-01 | 2020-11-10 | 上海应用技术大学 | Three-dimensional prismatic nickel cobaltate/silicon dioxide nano composite material and preparation method thereof |
| CN112939097A (en) * | 2021-02-09 | 2021-06-11 | 中国科学院山西煤炭化学研究所 | Nickel cobaltate nano material and preparation method and application thereof |
| CN113683126A (en) * | 2021-08-12 | 2021-11-23 | 武汉理工大学 | Palladium-doped nickel-cobalt spinel and preparation method thereof |
| CN114284082A (en) * | 2021-12-30 | 2022-04-05 | 江西科技师范大学 | Preparation method and application of high-capacitance oxygen vacancy rare earth doped cobaltosic oxide nanosheet |
| CN114864902A (en) * | 2022-05-27 | 2022-08-05 | 集美大学 | Lithium-sulfur battery positive electrode material and preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618869A (en) * | 2009-07-28 | 2010-01-06 | 中国科学院上海硅酸盐研究所 | Method for preparing small-size meso-porous hollow carbon sphere |
| CN102060300A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Method for synthesizing high-dispersibility high-specific surface area large-pore volume SiO2 hollow spheres |
| CN102381715A (en) * | 2010-09-03 | 2012-03-21 | 中国科学院上海硅酸盐研究所 | Large-pore-wall cage-shaped silica hollow sphere and preparation method thereof |
| CN104900420A (en) * | 2015-04-03 | 2015-09-09 | 中南大学 | NiCo2O4@MOx material of hollow core-shell structure and preparation and application methods thereof |
-
2017
- 2017-08-15 CN CN201710695235.0A patent/CN107452512A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618869A (en) * | 2009-07-28 | 2010-01-06 | 中国科学院上海硅酸盐研究所 | Method for preparing small-size meso-porous hollow carbon sphere |
| CN102060300A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Method for synthesizing high-dispersibility high-specific surface area large-pore volume SiO2 hollow spheres |
| CN102381715A (en) * | 2010-09-03 | 2012-03-21 | 中国科学院上海硅酸盐研究所 | Large-pore-wall cage-shaped silica hollow sphere and preparation method thereof |
| CN104900420A (en) * | 2015-04-03 | 2015-09-09 | 中南大学 | NiCo2O4@MOx material of hollow core-shell structure and preparation and application methods thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655120A (en) * | 2019-11-13 | 2020-01-07 | 东北电力大学 | Preparation method of mesoporous spherical nickel cobaltate nano material |
| CN110655120B (en) * | 2019-11-13 | 2022-03-25 | 东北电力大学 | Preparation method of mesoporous spherical nickel cobaltate nano material |
| CN111908522A (en) * | 2020-09-01 | 2020-11-10 | 上海应用技术大学 | Three-dimensional prismatic nickel cobaltate/silicon dioxide nano composite material and preparation method thereof |
| CN111908522B (en) * | 2020-09-01 | 2022-10-14 | 上海应用技术大学 | Three-dimensional prismatic nickel cobaltate/silicon dioxide nano composite material and preparation method thereof |
| CN112939097A (en) * | 2021-02-09 | 2021-06-11 | 中国科学院山西煤炭化学研究所 | Nickel cobaltate nano material and preparation method and application thereof |
| CN112939097B (en) * | 2021-02-09 | 2023-03-28 | 中国科学院山西煤炭化学研究所 | Nickel cobaltate nano material and preparation method and application thereof |
| CN113683126A (en) * | 2021-08-12 | 2021-11-23 | 武汉理工大学 | Palladium-doped nickel-cobalt spinel and preparation method thereof |
| CN113683126B (en) * | 2021-08-12 | 2022-09-13 | 武汉理工大学 | Palladium-doped nickel-cobalt spinel and preparation method thereof |
| CN114284082A (en) * | 2021-12-30 | 2022-04-05 | 江西科技师范大学 | Preparation method and application of high-capacitance oxygen vacancy rare earth doped cobaltosic oxide nanosheet |
| CN114284082B (en) * | 2021-12-30 | 2023-04-28 | 江西科技师范大学 | Preparation method and application of high-capacitance oxygen vacancy rare earth doped cobaltosic oxide nano-sheet |
| CN114864902A (en) * | 2022-05-27 | 2022-08-05 | 集美大学 | Lithium-sulfur battery positive electrode material and preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107452512A (en) | A kind of preparation method of hollow cobalt acid nickel for electrode material for super capacitor | |
| CN103318978B (en) | Preparation method of mesoporous nickel cobaltate fiber and application thereof | |
| CN102891016B (en) | A kind of cobalt acid nickel graphene composite material and application thereof and preparation method | |
| CN102107909B (en) | Method for preparing mesoporous nano manganese dioxide | |
| CN105289433B (en) | A kind of method of prepare with scale transition metal oxide porous microsphere | |
| CN104773764A (en) | Preparation method of three-dimensional flower-shaped nickel cobaltate nano-sheet mesoporous microspheres | |
| CN104821238A (en) | Method for preparing electrode material molybdate for super capacitor and application thereof | |
| CN104505508A (en) | Preparation method of nickel cobalt oxide electrode material | |
| CN103107025A (en) | Preparation method of supercapacitor electrode material NiCo2O4 | |
| CN108493458B (en) | High-performance echinoid nickel oxide/nickel cobaltate microsphere lithium oxygen battery positive electrode catalytic material and preparation method thereof | |
| CN105185604B (en) | A kind of preparation method and application of flexible electrode | |
| CN107792887A (en) | A kind of high-specific surface area ZnMn2O4Preparation method | |
| CN106876676B (en) | NiS classification micron ball of carbon shell cladding and its preparation method and application | |
| CN106876682A (en) | A kind of manganese oxide with loose structure/nickel micron ball and its preparation and application | |
| CN105449230B (en) | A kind of LaCoO3/ N-rGO compounds and its methods for making and using same | |
| CN107176620A (en) | A kind of method for preparing different morphologies transition metal oxide electrode material | |
| CN103219169A (en) | Preparation method for carbon-coated nickel oxide NiO/C as supercapacitor electrode material | |
| CN104291382A (en) | Preparation method of lanthanum ferrite porous micro-spheres | |
| CN107123555A (en) | Empty nanotube and its preparation method and application in a kind of metal hydroxides | |
| CN106847530A (en) | A kind of nickel cobalt base-carbon nano tube combination electrode material and preparation method thereof | |
| CN108597891A (en) | Composite material and preparation method and application are covered in a kind of double load double-contractings of silica@metal oxides/graphene aerogel | |
| CN106449136B (en) | Alpha-nickel hydroxide cobalt electrode material and the preparation method and application thereof | |
| Wei et al. | Transition metal oxide hierarchical nanotubes for energy applications | |
| CN105869907A (en) | Preparation method of carbon-nitrogen-codoped NiFe2O4-Ni nanocomposite material with cubic structure | |
| CN106964362A (en) | Metal molybdate/carbon composite nano-fiber and preparation method thereof and composite and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171208 |
|
| RJ01 | Rejection of invention patent application after publication |