CN106783208A - A kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance - Google Patents
A kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance Download PDFInfo
- Publication number
- CN106783208A CN106783208A CN201611222059.0A CN201611222059A CN106783208A CN 106783208 A CN106783208 A CN 106783208A CN 201611222059 A CN201611222059 A CN 201611222059A CN 106783208 A CN106783208 A CN 106783208A
- Authority
- CN
- China
- Prior art keywords
- mesoporous
- cobalt
- unformed
- preparation
- cobalt ferrite
- 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
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 86
- 239000010941 cobalt Substances 0.000 title claims abstract description 86
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 58
- 239000007772 electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 22
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000006230 acetylene black Substances 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 11
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 208000011580 syndromic disease Diseases 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 210000004754 hybrid cell Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance, step is as follows：The preparation of step 1, cobalt ferrite precursor solution；The preparation of step 2, ferrous acid cobalt precursor；The preparation of step 3, mesoporous unformed cobalt ferrite；The preparation of step 4, mesoporous unformed cobalt ferrite electrode material.The inventive method experiment condition is gently controllable, practical, and favorable reproducibility, environmental protection, and raw material be easy to get, low cost.The material is expected to be applied to the field such as capacitor area and electrochemical sensing, detection.The preparation method is simple and easy to apply, general, is expected to realize industrialized application.
Description
Technical field
The invention belongs to electrode for super capacitor technical field of material, and in particular to a kind of new is based on
The preparation method of the mesoporous unformed cobalt ferrite electrode material of high-performance.
Background technology
Ultracapacitor is after the energy storage device of new generation occurred after chemical cell, fuel cell, hybrid power product, tool
There are energy density high, long lifespan, charge the advantage such as fast.Its power density and energy density between traditional capacitor and battery it
Between, and its cyclical stability has larger lifting to improve compared with battery, thus receive much concern.Research discovery, determines ultracapacitor
The good and bad key of performance is electrode material.Electrode material is divided into two classes by people according to the difference of energy storage principle：One class is double electricity
Layer material, this kind of material conductivity, cyclicity are good but specific capacitance is relatively low.Another kind of is fake capacitance material, this kind of material specific capacitance
High but conductance is low, cyclical stability is poor.Therefore, the elements such as cheap Ni, Co, Fe with redox property are developed
High performance electrode material be just of concern.
The performance of electrode material depends on the arrangement of construction unit, the specific surface area of material and the electrode material and electricity of material
Solve the factors such as the wellability of liquid, the electric conductivity of electrode material, the quantity in electro-chemical activity site.In recent years, composite transition metal
Oxide, for example：The composite oxides research report of ferrite, cobaltatess and manganate etc. is numerous, especially in photoelectrocatalysis, life
The fields such as thing sensing, microelectronic component, ultracapacitor, lithium ion battery show huge application prospect.Wherein, cobalt ferrite
In being widely used for the fields such as catalysis, hydrogen reduction, sensor and ultracapacitor.However, the cobalt ferrite of nearly all report
Electrode material is all crystal, and its specific surface area, electrolyte wellability still need to increase substantially.
Current research is explicitly pointed out, and the electrode material of mesoporous undefined structure can greatly improve its chemical property.It is dashed forward
The advantage for going out is summarized as follows：(1) with big specific surface area, effective contact area of electrolyte and active material can be improved；
(2) meso-hole structure can improve the diffusion path of electrolyte；(3) undefined structure is conducive to the abundant infiltration of electrolyte.To sum up
Described, the chemical property of mesoporous unformed electrode material is expected to be not fully exerted.
The content of the invention
The purpose of the present invention aims to provide a kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance.
To achieve the above object, the technical solution adopted by the present invention is by a certain amount of cobalt nitrate, ferric nitrate, sodium citrate
Powder add distilled water, be well mixed, sol gel reaction is carried out at low temperature and obtains solid precursor, it is scrubbed, dry
Last calcining in tube furnace is obtained.
Concrete technical scheme is as follows：
A kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance, step is as follows：
The preparation of step 1, cobalt ferrite precursor solution：
Soluble cobalt, soluble ferric iron salt, sodium citrate are added in distilled water, ultrasound in Ultrasound Instrument is put into, magnetic is used
Power agitator stirs, then stand-by, obtains cobalt ferrite precursor solution；
The preparation of step 2, ferrous acid cobalt precursor：
The cobalt ferrite precursor solution that step 1 is obtained is warmed up to 60 DEG C under continuous stirring, maintains 60 DEG C of reactions 1 small
When, then proceed to be warmed up to 90 DEG C and react 24 hours；After treating that solvent is evaporated, and reactant is changed into drying solid, stop heating；It is cold
But to room temperature, washing, vacuum drying obtain final product ferrous acid cobalt precursor；
The preparation of step 3, mesoporous unformed cobalt ferrite：
Step 2 gained ferrous acid cobalt precursor is put into tube furnace and is calcined, after the completion of calcining, obtain mesoporous unformed
Cobalt ferrite；
The preparation of step 4, mesoporous unformed cobalt ferrite electrode material：
The foam nickel sheet that will have been bought cuts into the fritter of 5 centimetres of 1 cm x, then it is respectively placed in acetone successively molten
It is in liquid, dilute hydrochloric acid solution, the aqueous solution and ultrasonically treated；Vacuum drying is placed in after being disposed, it is stand-by；
The mesoporous unformed cobalt ferrite of step 3 gained is uniformly mixed with acetylene black, polytetrafluoroethylene (PTFE) by proportioning, one kind is obtained
Sticky slurry, then slurry is applied in the foam nickel sheet handled well, finally dry, obtain mesoporous unformed ferrous acid cobalt electrode
Material.
In step 1, the substance withdrawl syndrome of the soluble cobalt, soluble ferric iron salt, sodium citrate in distilled water it
Than being 1~10:2~20:5~50, the substance withdrawl syndrome of soluble cobalt is 12.5~125mmol/L.
In step 1, the soluble cobalt is any one in cobalt chloride, cobalt nitrate, cobalt acetate, and soluble ferric iron salt is
Any one in iron chloride, ferric nitrate.
In step 1, the sodium citrate used as stabilizers or complexing agent of addition.
In step 3, the temperature of the calcining is 200~700 DEG C, is incubated 2~5h；Calcining programming rate be 1~5 DEG C/
min。
In step 4, the mesoporous unformed cobalt ferrite is 7 with the mass ratio of acetylene black, polytetrafluoroethylene (PTFE):2:1.
In step 4, the mesoporous unformed cobalt ferrite is 8 with the mass ratio of acetylene black, polytetrafluoroethylene (PTFE):1:1.
In step 4, the drying temperature is 60~150 DEG C, and drying time is 3~6h.
Beneficial effect：
The inventive method experiment condition is gently controllable, practical, and favorable reproducibility, environmental protection, and raw material be easy to get,
Low cost.The material is expected to be applied to the field such as capacitor area and electrochemical sensing, detection.The preparation method is simply easy
It is capable, general, it is expected to realize industrialized application.
Brief description of the drawings
Fig. 1 is the gained crystal structure cobalt ferrite of the embodiment of the present invention 1 (curve a) and mesoporous unformed cobalt ferrite (curve b)
X-ray powder diffraction analysis chart (XRD)；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the mesoporous unformed cobalt ferrite of gained of the embodiment of the present invention 1；
Fig. 3 is the transmission electron microscope picture (TEM) of the mesoporous unformed cobalt ferrite of gained of the embodiment of the present invention 1；
Fig. 4 is the specific surface area figure (BET) of the mesoporous unformed cobalt ferrite of gained of the embodiment of the present invention 1；
Fig. 5 is the cycle charge discharge electrograph (CV) of the mesoporous unformed cobalt ferrite of gained of the embodiment of the present invention 1, wherein, curve a's
Sweep speed is 5mV/s, and the sweep speed of curve b is 10mV/s, and the sweep speed of curve c is 20mV/s.
Specific embodiment
The present invention is expanded on further below by example, but protection scope of the present invention is not limited to these examples.This
Raw material in invention example is purchased from Shanghai Chinese medicines group, is analysis pure.
Embodiment 1
The powder of the cobalt nitrate of 5mmol, the ferric nitrate of 10mmol, the sodium citrate of 15mmol is added into 80mL distilled water,
It is placed in 100ml beakers, is put into ultrasound 5 minutes in Ultrasound Instrument, is well mixed 30 minutes it with magnetic stirrer, then
It is stand-by.Above-mentioned cobalt ferrite precursor solution is warmed up to 60 degree under continuous stirring, reaction 1 hour under the conditions of maintaining 60 degree, so
It is follow-up continuous to be warmed up to 90 degree and react 24 hours.After treating that whole reaction solution is evaporated, and reactant is changed into drying solid, stop adding
Heat.And room temperature is cooled to, repeatedly washing, vacuum drying, obtain final product ferrous acid cobalt precursor；Above-mentioned ferrous acid cobalt precursor is put into tubular type
Calcined at 300 DEG C in stove, calcinating speed is 1 degree per minute, is incubated 2 hours.Obtain mesoporous unformed cobalt ferrite.In Fig. 1 a
Each diffraction maximum position and relative intensity match with JPCDS cards (79-1744), show the ferrous acid that product is spinel structure
Cobalt.The XRD that the sample is found in Fig. 1 b is the Bao Feng of softening, it was demonstrated that the sample for obtaining is undefined structure.As can be seen from Figure 2
The sample for obtaining is the uneven particle population of shape.The unformed cobalt ferrite for preparing as can be seen from Figure 3 is loose porous
Structure.Fig. 4 is nitrogen adsorption desorption curve, and the sample for as can be seen from the figure preparing is meso-hole structure, and is calculated its hole
Footpath is about 5.4nm.By the mesoporous unformed cobalt ferrite of gained and acetylene black, polytetrafluoroethylene (PTFE) in certain mass ratio 7:2:1 is equal
Even mixing, obtains a kind of sticky slurry, then slurry is applied in above-mentioned ready foam nickel sheet, finally in 60 degree of dryings
It is cooled to room temperature within 6 hours, obtains electrode material.Its chemical property is tested under three-electrode system.Fig. 5 is followed for electrode material
Ring volt-ampere curve, therefrom it can be found that the mesoporous unformed electrode material has good electrochemical capacitor characteristic and ratio higher
Capacity.
Embodiment 2
The powder of the cobalt nitrate of 1mmol, the ferric nitrate of 2mmol, the sodium citrate of 5mmol is added into 80ml distilled water, is put
In 100ml beakers, ultrasound 5 minutes in Ultrasound Instrument are put into, are well mixed 30 minutes it with magnetic stirrer.Gradually rise
Temperature is maintained 1 hour to 60 degree, is reacted 24 hours after then proceeding to be warmed up to 90 degree.Treat that whole reaction solution is evaporated, and reactant
After being changed into drying solid, stop heating.And room temperature is cooled to, repeatedly washing, vacuum drying, obtain final product ferrous acid cobalt precursor；Will be upper
State during ferrous acid cobalt precursor is put into tube furnace and calcined at 350 DEG C, calcinating speed is 1.5 degree per minute, is incubated 2 hours.
To mesoporous unformed cobalt ferrite.By the mesoporous unformed cobalt ferrite of gained and acetylene black, polytetrafluoroethylene (PTFE) in certain mass ratio 8:
1:1 uniform mixing, obtains a kind of sticky slurry, then slurry is applied in above-mentioned ready foam nickel sheet, finally 100
Degree drying is cooled to room temperature in 4 hours, finally gives cobalt ferrite electrode material.
Embodiment 3
The powder of the cobalt chloride of 10mmol, the iron chloride of 20mmol, the sodium citrate of 50mmol is added into 80ml distilled water,
It is placed in 100ml beakers, is put into ultrasound 5 minutes in Ultrasound Instrument, is well mixed 30 minutes it with magnetic stirrer.Gradually
It is warmed up to 60 degree to maintain 1 hour, then proceedes to be warmed up to 90 degree and react 24 hours.Treat that whole reaction solution is evaporated, and reactant
After being changed into drying solid, stop heating.And room temperature is cooled to, repeatedly washing, vacuum drying, obtain final product ferrous acid cobalt precursor；Will be upper
State during ferrous acid cobalt precursor is put into tube furnace and calcined at 200 DEG C, calcinating speed is 2 degree per minute, is incubated 2 hours.Obtain
Mesoporous unformed cobalt ferrite.By the mesoporous unformed cobalt ferrite of gained and acetylene black, polytetrafluoroethylene (PTFE) in certain mass ratio 8:1:1
Uniform mixing, obtains a kind of sticky slurry, then slurry is applied in above-mentioned ready foam nickel sheet, finally at 120 degree
Drying is cooled to room temperature in 3 hours, finally gives cobalt ferrite electrode material.
Embodiment 4
The powder of the cobalt acetate of 3mmol, the ferric nitrate of 6mmol, the sodium citrate of 10mmol is added into 80ml distilled water, is put
In 100ml beakers, ultrasound 5 minutes in Ultrasound Instrument are put into, are well mixed 30 minutes it with magnetic stirrer.Gradually rise
Temperature is maintained 1 hour to 60 degree, is reacted 24 hours after then proceeding to be warmed up to 90 degree.Treat that whole reaction solution is evaporated, and reactant
After being changed into drying solid, stop heating.And room temperature is cooled to, repeatedly washing, vacuum drying, obtain final product ferrous acid cobalt precursor；Will be upper
State during ferrous acid cobalt precursor is put into tube furnace and calcined at 700 DEG C, calcinating speed is 5 degree per minute, is incubated 1 hour.Obtain
Mesoporous unformed cobalt ferrite.By the mesoporous unformed cobalt ferrite of gained and acetylene black, polytetrafluoroethylene (PTFE) in certain mass ratio 7:2:1
Uniform mixing, obtains a kind of sticky slurry, then slurry is applied in above-mentioned ready foam nickel sheet, finally at 150 degree
Drying is cooled to room temperature in 2 hours, finally gives cobalt ferrite electrode material.
Embodiment 5
The powder of the cobalt chloride of 5mmol, the iron chloride of 10mmol, the sodium citrate of 15mmol is added into 80ml distilled water,
It is placed in 100ml beakers, is put into ultrasound 5 minutes in Ultrasound Instrument, is well mixed 30 minutes it with magnetic stirrer.Gradually
It is warmed up to 60 degree to maintain 1 hour, then proceedes to be warmed up to 90 degree and react 24 hours.Treat that whole reaction solution is evaporated, and reactant
After being changed into drying solid, stop heating.And room temperature is cooled to, repeatedly washing, vacuum drying, obtain final product ferrous acid cobalt precursor；Will be upper
State during ferrous acid cobalt precursor is put into tube furnace and calcined at 450 DEG C, calcinating speed is 3 degree per minute, is incubated 5 hours.Obtain
Mesoporous unformed cobalt ferrite.By the mesoporous unformed cobalt ferrite of gained and acetylene black, polytetrafluoroethylene (PTFE) in certain mass ratio 8:1:1
Uniform mixing, obtains a kind of sticky slurry, then slurry is applied in above-mentioned ready foam nickel sheet, finally at 110 degree
Drying is cooled to room temperature in 5 hours, finally gives cobalt ferrite electrode material.
Claims (7)
1. a kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance, it is characterised in that step is as follows：
The preparation of step 1, cobalt ferrite precursor solution：
Soluble cobalt, soluble ferric iron salt, sodium citrate are added in distilled water, ultrasound in Ultrasound Instrument is put into, are stirred with magnetic force
Device is mixed to stir, it is then stand-by, obtain cobalt ferrite precursor solution；
The preparation of step 2, ferrous acid cobalt precursor：
The cobalt ferrite precursor solution that step 1 is obtained is warmed up to 60 DEG C under continuous stirring, maintains 60 DEG C to react 1 hour, so
It is follow-up continuous to be warmed up to 90 DEG C and react 24 hours；After treating that solvent is evaporated, and reactant is changed into drying solid, stop heating；It is cooled to
Room temperature, washing, vacuum drying, obtains final product ferrous acid cobalt precursor；
The preparation of step 3, mesoporous unformed cobalt ferrite：
Step 2 gained ferrous acid cobalt precursor is put into tube furnace and is calcined, after the completion of calcining, obtain mesoporous unformed ferrous acid
Cobalt；
The preparation of step 4, mesoporous unformed cobalt ferrite electrode material：
Foam nickel sheet is cut into the fritter of 5 centimetres of 1 cm x, then it is respectively placed in acetone soln, watery hydrochloric acid successively molten
It is in liquid, the aqueous solution and ultrasonically treated；Vacuum drying is placed in after being disposed, it is stand-by；
The mesoporous unformed cobalt ferrite of step 3 gained is uniformly mixed with acetylene black, polytetrafluoroethylene (PTFE) by proportioning, obtains a kind of sticky
Slurry, then slurry is applied in the foam nickel sheet handled well, finally dry, obtain mesoporous unformed ferrous acid cobalt electrode material
Material.
2. a kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance according to claim 1, its
Be characterised by, in step 1, the substance withdrawl syndrome of the soluble cobalt, soluble ferric iron salt, sodium citrate in distilled water it
Than being 1~10:2~20:5~50, the substance withdrawl syndrome of soluble cobalt is 12.5~125mmol/L.
3. a kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance according to claim 1 and 2,
Characterized in that, in step 1, the soluble cobalt is any one in cobalt chloride, cobalt nitrate, cobalt acetate, soluble iron
Salt is any one in iron chloride, ferric nitrate.
4. a kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance according to claim 1, its
It is characterised by, in step 3, the temperature of the calcining is 200~700 DEG C, is incubated 2~5h；Calcining programming rate be 1~5 DEG C/
min。
5. a kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance according to claim 1, its
It is characterised by, in step 4, the mesoporous unformed cobalt ferrite is 7 with the mass ratio of acetylene black, polytetrafluoroethylene (PTFE):2:1.
6. a kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance according to claim 1, its
It is characterised by, in step 4, the mesoporous unformed cobalt ferrite is 8 with the mass ratio of acetylene black, polytetrafluoroethylene (PTFE):1:1.
7. a kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance according to claim 1, its
It is characterised by, in step 4, the drying temperature is 60~150 DEG C, and drying time is 3~6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611222059.0A CN106783208A (en) | 2016-12-27 | 2016-12-27 | A kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611222059.0A CN106783208A (en) | 2016-12-27 | 2016-12-27 | A kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106783208A true CN106783208A (en) | 2017-05-31 |
Family
ID=58925824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611222059.0A Pending CN106783208A (en) | 2016-12-27 | 2016-12-27 | A kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106783208A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109994321A (en) * | 2019-03-22 | 2019-07-09 | 江苏大学 | A kind of preparation method of carbon cloth base cobalt acid iron/molybdenum disulfide hierarchical structure electrode material |
| CN114345347A (en) * | 2022-01-20 | 2022-04-15 | 陕西科技大学 | Cobalt ferrite cocatalyst, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275999A (en) * | 2011-05-27 | 2011-12-14 | 山东大学 | Network cobalt ferrite for anode material for lithium ion battery and use thereof |
| CN102769128A (en) * | 2011-05-04 | 2012-11-07 | 三星电子株式会社 | Electrode active material, preparation method thereof, and electrode and lithium battery containing the same |
| CN104332625A (en) * | 2014-08-27 | 2015-02-04 | 山东大学 | Cobalt ferrite-nitrogen doped carbon composite negative electrode material for dynamic lithium battery and preparation method thereof |
| CN104852042A (en) * | 2014-12-20 | 2015-08-19 | 青岛科技大学 | Preparation method and application of cobalt-iron composite oxide nanorods for lithium ion battery anode material |
-
2016
- 2016-12-27 CN CN201611222059.0A patent/CN106783208A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102769128A (en) * | 2011-05-04 | 2012-11-07 | 三星电子株式会社 | Electrode active material, preparation method thereof, and electrode and lithium battery containing the same |
| CN102275999A (en) * | 2011-05-27 | 2011-12-14 | 山东大学 | Network cobalt ferrite for anode material for lithium ion battery and use thereof |
| CN104332625A (en) * | 2014-08-27 | 2015-02-04 | 山东大学 | Cobalt ferrite-nitrogen doped carbon composite negative electrode material for dynamic lithium battery and preparation method thereof |
| CN104852042A (en) * | 2014-12-20 | 2015-08-19 | 青岛科技大学 | Preparation method and application of cobalt-iron composite oxide nanorods for lithium ion battery anode material |
Non-Patent Citations (1)
| Title |
|---|
| SHUQUAN HUANG, YUANGUO XU, MENG XIE .ETC: "Synthesis of magnetic CoFe2O4/g-C3N4 composite and its enhancement of photocatalytic ability under visible-light", 《 COLLOIDS AND SURFACES A》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109994321A (en) * | 2019-03-22 | 2019-07-09 | 江苏大学 | A kind of preparation method of carbon cloth base cobalt acid iron/molybdenum disulfide hierarchical structure electrode material |
| CN109994321B (en) * | 2019-03-22 | 2020-12-18 | 江苏大学 | Preparation method of carbon cloth-based ferric cobaltate/molybdenum disulfide hierarchical structure electrode material |
| CN114345347A (en) * | 2022-01-20 | 2022-04-15 | 陕西科技大学 | Cobalt ferrite cocatalyst, and preparation method and application thereof |
| CN114345347B (en) * | 2022-01-20 | 2024-05-14 | 陕西科技大学 | Cobalt ferrite cocatalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107731566A (en) | A kind of preparation method and application of three-dimensional petal-shaped nickel cobalt sulfide electrode material | |
| CN106229503B (en) | A kind of preparation method of nickel oxide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery | |
| CN104773764A (en) | Preparation method of three-dimensional flower-shaped nickel cobaltate nano-sheet mesoporous microspheres | |
| CN105529472A (en) | Co-N double-doped flaky porous two-dimensional carbon material and preparation method thereof | |
| CN108962632B (en) | Preparation method of graphene/nitrogen-doped carbon/nickel oxide composite material | |
| CN107705998A (en) | A kind of ferrite@graphenes hydrogel composite material and its application in electrochemical energy storage field | |
| CN106971855B (en) | A kind of nickel ferrite based magnetic loaded nanoparticle electrode material and preparation method and purposes | |
| CN110581264B (en) | High-performance nickel-zinc battery negative electrode active material and preparation method thereof | |
| CN105845904B (en) | A kind of sodium-ion battery metal oxide/polypyrrole hollow nanotube anode material and preparation method thereof | |
| CN106898503A (en) | A kind of cobalt acid nickel/cobalt sulfide nickel nano composite material of bar-shaped core shell structure, preparation method and applications | |
| CN109546162A (en) | A kind of recyclable preparation method of microporous iron-nitrogen-doped carbon catalyst material | |
| CN110980673B (en) | Metal phosphide, preparation method thereof and application thereof in super capacitor | |
| CN108439370A (en) | A kind of preparation method and its usage of two dimension porous boron nitrogen codope carbon nanomaterial | |
| CN105140494A (en) | Biomimetic synthesis method of Fe3O4/Fe/C nano composite battery electrode material | |
| CN102412400A (en) | Silver vanadium oxide / polymer three coaxial nanowire and preparation method and application thereof | |
| CN102969164B (en) | Preparation of cobalt-bismuth composite oxide and application of cobalt-bismuth composite oxide in preparation of super capacitor electrode | |
| CN107321372A (en) | The preparation method of CoS nano particles/N doping RGO liberation of hydrogen composites | |
| CN110655120B (en) | Preparation method of mesoporous spherical nickel cobaltate nano material | |
| CN107275627A (en) | Mn doping hollow porous classifying nano ball electrode materials of CuS and its preparation method and application | |
| CN110491684A (en) | Needle-shaped colored cobalt nickel bimetal hydroxide composite material and its preparation method and application | |
| CN101872651B (en) | Method for preparing in-situ self-grown nano carbon composite material | |
| CN106783208A (en) | A kind of preparation method based on the mesoporous unformed cobalt ferrite electrode material of high-performance | |
| CN103578772B (en) | Electrode for capacitors active material and preparation method thereof | |
| CN106340403A (en) | Preparation method and purpose of zinc cobaltate nano wire or nanometer band electrode material | |
| CN104037389B (en) | Preparation method of transition metal oxide lithium ion battery cathode material |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |