CN109256279A - A kind of graphene and Co3O4The preparation method of composite material - Google Patents
A kind of graphene and Co3O4The preparation method of composite material Download PDFInfo
- Publication number
- CN109256279A CN109256279A CN201710575852.7A CN201710575852A CN109256279A CN 109256279 A CN109256279 A CN 109256279A CN 201710575852 A CN201710575852 A CN 201710575852A CN 109256279 A CN109256279 A CN 109256279A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- solution
- graphene oxide
- composite material
- 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
- H01G11/24—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
- H01G11/22—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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/84—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
-
- 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 present invention relates to supercapacitor conductive material preparation technical field, specifically a kind of graphene and Co3O4The preparation method of composite material, which is characterized in that specific step is as follows: graphene oxide ultrasound pretreatment；Precipitating reagent and surfactant is added；Hydro-thermal or solvent thermal reaction are carried out in water heating kettle, obtain gel after cooling；Then washes clean is freeze-dried under vacuum conditions again, obtain Co3O4It is dispersed in graphene/Co of the morphology controllable in graphene base body3O4Composite material.The technical advantages of the present invention are that graphene/Co of morphology controllable has been made by hydro-thermal or solvent thermal reaction using different precipitating reagent and suitable surfactant3O4Composite material, specific capacitance with higher and good charge and discharge cycles stability；Co3O4It is evenly distributed；Different patterns directly results in different initial specific capacities and different stable circulation performance performances；The temperature of reaction is lower, high-efficient.
Description
Technical field
The present invention relates to supercapacitor conductive material preparation technical field, specifically a kind of graphene and Co3O4It is multiple
The preparation method of condensation material.
Background technique
With gradually protruding for our times energy problem and environmental problem, people are in research renewable energy or cleaning energy
Huge effort has been made in source etc., in the extension process of these new energies, efficient energy conversion be to
It closes important.Supercapacitor has many advantages, such as high power density, the cycle life of overlength and quick charge-discharge velocity, gradually
The huge concern of people is caused, especially there is boundless answer in electronics, industry, energy management and military equipment field
Use prospect.The performance of electrode material is the key factor of supercapacitor chemical property, the performance of electrode material and active material
The size and electric conductivity of material have very close relationship.
The most wide electrode material of research includes carbon material, transition metal oxide and conducting polymer at present.Transition metal
Co in oxide3O4There is many advantages, such as specific capacitance is high, resourceful, cheap, environmental-friendly.And graphene is one
Kind sp2The two-dimensional material of the carbon atom composition of hydridization, specific surface area and good electric conductivity with super large, and have very high
Flexibility, by itself and Co3O4It is prepared into composite material, conductive network, fixed Co can be not only provided3O4, and as super
When the electrode material of capacitor, can effectively be buffered in charge and discharge process causes active material from collection due to volume change
It falls off on fluid, greatly reduces the cyclical stability of material.
Co3O4Lead to activity in the very easy reunion of process of preparation nano material with quite high theoretical specific capacity
Substance easily falls off on a current collector, the strong influence chemical property of composite material, therefore cannot separately as super electricity
The electrode material of container.Prepare uniform graphene/Co3O4Composite material, give full play to the big specific surface area of graphene and
Co3O4High capacity be one very with application value project.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide uniform graphene/Co3O4The preparation of composite material
Method is prepared by hydro-thermal reaction at a proper temperature by using different precipitating reagent and suitable surfactant
To ordered graphene/Co of morphology controllable3O4Composite material, such as it is flower-shaped, rodlike or spherical；And it can be different by control growth
Pattern adjust the chemical property of composite material.
To achieve the above object, a kind of graphene and Co are designed3O4The preparation method of composite material, which is characterized in that specific
Steps are as follows:
1), graphene oxide ultrasound pre-processes: graphene oxide solution is added in cobalt salt while stirring, then ultrasonic disperse
Uniformly, solution A is obtained；
2) precipitating reagent and surfactant, are added in solution A, stirs evenly, then the isothermal holding at 0~80 DEG C
30min~4h obtains solution B；The precipitating reagent is any one in sodium hydroxide, urea element or methenamine；
3), solution B is transferred in the water heating kettle of polytetrafluoroethyllining lining, at a temperature of 140~300 DEG C carry out hydro-thermal or
10~20h of solvent thermal reaction, after reaction, natural cooling obtains gel；
4), by gained gel deionized water and/or dehydrated alcohol washes clean, then freezing is dry under vacuum conditions again
It is dry, obtain Co3O4It is dispersed in the graphene and Co of the morphology controllable in graphene base body3O4Composite material.
The concentration of graphene oxide solution described in step 1) is 0.1~5mg/mL, surfactant and graphene oxide
The mass ratio of graphene oxide in solution is 1: 0.51: 5 or 1: 1~1: 10.
The graphene oxide ultrasound pretreated time is 10~60min, and the rate of stirring is 100~600rad/
Min, ultrasonic power are 150~1000W.
Cobalt salt described in step 1) is one of cobalt chloride, cobalt nitrate, cobalt acetate, cobaltous sulfate.
In step 1), the mass ratio of the graphene oxide in the cobalt salt and graphene oxide solution is 10: 1~30: 1.
In step 2), the mass ratio of the precipitating reagent and cobalt salt is 1: 0.1~1: 5.
In step 2), the surfactant is polyvinyl lactam PEI, PVAC polyvinylalcohol or polyvinylpyrrolidine
Any one of ketone PVP.
When in step 3) using solvent heat, solvent uses dehydrated alcohol, dimethyl sulfoxide or n,N-Dimethylformamide.
When the volume filling degree of water heating kettle in step 3) is 30%~90%, heating rate is 3~15 DEG C/min, when reaction
Between be 8~16 hours.
In step 4), obtained gel using alternately washing 2~4 times of dehydrated alcohol and water, the temperature of freeze-drying is-
120~-50 DEG C, vacuum degree is at least 1 × 10-2Pa, the time of freeze-drying are 48~96 hours.
The technical advantages of the present invention are that using different precipitating reagent and suitable surfactant, by hydro-thermal or
The graphene and Co of morphology controllable has been made in solvent thermal reaction3O4Composite material；And the precipitating reagent selected is cheap and easy to get, pattern
Regulating effect is obvious, Co3O4It is evenly distributed；Different patterns directly results in different initial specific capacities and different stable circulations
Performance provides a kind of convenient method to control the performance of material；The graphene and Co of the different-shape of preparation3O4It is multiple
Condensation material, specific capacitance with higher and good charge and discharge cycles stability；The temperature of reaction is relatively low, high-efficient.
Detailed description of the invention
Fig. 1 is flow diagram prepared by the present invention.
Fig. 2 is graphene/Co of the three-dimensional appearance prepared in the embodiment of the present invention 13O4Composite material scanning electron microscope (SEM) photograph.
Fig. 3 is graphene/Co of the sheet pattern prepared in the embodiment of the present invention 23O4The scanning electron microscope of composite material
Figure.
Fig. 4 is graphene/Co of the spherical morphology prepared in the embodiment of the present invention 33O4The scanning electron microscope (SEM) photograph of composite material.
Fig. 5 is graphene/Co of three-dimensional appearance in the embodiment of the present invention 13O4The X-ray diffractogram of composite material.
Fig. 6 is graphene/Co of three kinds of patterns in the embodiment of the present invention 1,2,3,43O4Electric current of the composite material in 1.5A/g
Resulting charging and discharging curve figure under density.
Specific embodiment
The present invention is further described now in conjunction with accompanying drawings and embodiments.
Embodiment 1
Graphene and Co are prepared by the step in Fig. 13O4Composite material, the specific steps are as follows:
1) graphene oxide solution that 90mL concentration is 0.5g/mL is prepared, 20min is ultrasonically treated, obtains homogeneous and transparent
Colloidal solution.Four water cobalt acetate 1.2g are weighed, are slowly added in colloidal solution while stirring, control revolving speed is 200r/min, is surpassed
Sonication 30min, obtains solution A.
2) into solution A be added 0.6mg sodium hydroxide solution and 15mg is added PEI as surfactant, stir
It mixes uniformly, keeps the temperature 1h at 5 DEG C, obtain solution B.
3) solution B being transferred to 100mL polytetrafluoroethylene (PTFE) as in the stainless steel water heating kettle of liner, heating rate is 10 DEG C/
Min is kept for 15 hours in 150 DEG C of constant temperature, gel is then obtained after natural cooling.
4) gel is washed with deionized three times, and is 2 × 10 in vacuum degree-3Under conditions of Pa, freezed with -110 DEG C
The graphene and Co of the dry 72 hours patterns to get three-dimensional flower shape3O4Composite material, referring to fig. 2.
Resulting materials are uniformly mixed with PVDF and conductive black according to 9: 1.5: 0.5 mass ratio, nickel foam is coated in
About 1cm on collector2, using 6mol/L potassium hydroxide solution as electrolyte, after charge and discharge 2 times, measure in 1.5A/g electricity
Flowing down capacity is more than 763F/g.Metal oxide in composite material obtained in this example is determined using Rigaku X-ray diffractometer
Crystallinity and crystal form, as shown in figure 5, it can be observed that the apparent characteristic peak of cobalt hydroxide and the characteristic peak of graphene.
Embodiment 2
1) graphene oxide solution that 90mL concentration is 0.2g/mL is prepared, 20min is ultrasonically treated, obtains homogeneous and transparent
Colloidal solution.Weigh cobalt chloride 1.2g, be slowly added in colloidal solution while stirring, control revolving speed be 300r/min, ultrasound at
30min is managed, solution A is obtained.
2) solution A is added to the urea element of 1.5g, and the PEI that 20mg is added is stirred evenly, as surfactant 50
1h is kept the temperature at DEG C, obtains solution B.
3) will solution B be transferred to 100mL polytetrafluoroethylene (PTFE) be used as in the stainless steel water heating kettle of liner, heating rate for 5 DEG C/
Min is kept for 15 hours in 160 DEG C of constant temperature, gel is then obtained after natural cooling.
4) gel is washed with deionized three times, and is 2 × 10 in vacuum degree-3It is freezed under conditions of Pa, with -110 DEG C
The dry 72 hours graphenes and Co to get sheet pattern3O4Composite material, referring to Fig. 3.
Sample preparation is same as Example 1 with test condition, and measuring the capacity under 1.5A/g electric current is 785F/g.
Embodiment 3
1) graphene oxide solution that 90mL concentration is 0.25g/mL is prepared, 20min is ultrasonically treated, obtains homogeneous and transparent
Colloidal solution.Weigh cobalt chloride 1.2g, be slowly added in colloidal solution while stirring, control revolving speed be 300r/min, ultrasound at
30min is managed, solution A is obtained.
2) the urea element of 1.5g is added to solution A, and 15mg polyvinyl alcohol is added as surfactant, stirs evenly,
1h is kept the temperature at 70 DEG C, obtains solution B.
3) solution B being transferred to 100mL polytetrafluoroethylene (PTFE) as in the stainless steel water heating kettle of liner, heating rate is 10 DEG C/
Min is kept for 12 hours in 180 DEG C of constant temperature, gel is then obtained after natural cooling.
4) gel is washed with deionized three times, and is 2 × 10 in vacuum degree-3It is small with -100 DEG C 48 under conditions of Pa
When to get spherical morphology graphene and Co3O4Composite material, referring to fig. 4.
Sample preparation is same as Example 1 with test condition, and measuring the capacity under 1.5A/g electric current is 787F/g.
Embodiment 4:
1) graphene oxide solution that 90mL concentration is 0.2g/mL is prepared, 30min is ultrasonically treated, obtains homogeneous and transparent
Colloidal solution.Weigh cobaltous sulfate 1.5g, be slowly added in colloidal solution while stirring, control revolving speed be 300r/min, ultrasound at
30min is managed, solution A is obtained.
2) 1.5g urea element is added into solution A, and 15mg polyvinyl alcohol is added as surfactant, stirs evenly,
1.5h is kept the temperature at 60 DEG C, obtains solution B.
3) solution B being transferred to 100mL polytetrafluoroethylene (PTFE) as in the stainless steel water heating kettle of liner, heating rate is 5 DEG C/
Min is kept for 12 hours in 180 DEG C of constant temperature, gel is then obtained after natural cooling.
4) gel is washed with deionized three times, and is 2 × 10 in vacuum degree-3It is small with -100 DEG C 64 under conditions of Pa
When to get graphene and Co3O4Composite material.
Sample preparation is same as Example 1 with test condition, and measuring the capacity under 1.5A/g electric current is 722F/g.
A large amount of OH can be directly provided when sodium hydroxide is as precipitating reagent in the present invention-1, in first segment low-temperature treatment
Stable presoma easy to form in the process, Co in composite material3O4Shape comparison rule.And urea element and methenamine solution
It is to decompose slowly to provide OH in second segment pyroprocess-1, but the rate decomposed is different, the Co in composite material3O4It is easy
Form different three-dimensional structures.When using solvent thermal reaction, the polarity and boiling point of solvent also significantly affect Co3O4Growth.
The presoma that counter ion counterionsl gegenions difference in different cobalt salts is prepared, the polarity of counter ion counterionsl gegenions is weaker, and the reaction of second segment is nucleated temperature
It spends relatively lower.
Claims (10)
1. a kind of graphene and Co3O4The preparation method of composite material, which is characterized in that specific step is as follows:
1), graphene oxide ultrasound pre-processes: graphene oxide solution is added in cobalt salt while stirring, then ultrasonic disperse is equal
It is even, obtain solution A；
2) precipitating reagent and surfactant, are added in solution A, stirs evenly, then the isothermal holding 30min at 0~80 DEG C
~4h, obtains solution B；The precipitating reagent is any one in sodium hydroxide, urea element or methenamine；
3), solution B is transferred in the water heating kettle of polytetrafluoroethyllining lining, hydro-thermal or solvent are carried out at a temperature of 140~300 DEG C
10~20h of thermal response, after reaction, natural cooling obtains gel；
4) it, by gained gel deionized water and/or dehydrated alcohol washes clean, is then freeze-dried under vacuum conditions again,
Obtain Co3O4It is dispersed in the graphene and Co of the morphology controllable in graphene base body3O4Composite material.
2. preparation method according to claim 1, it is characterised in that: the concentration of graphene oxide solution described in step 1)
For 0.1~5mg/mL, the mass ratio of the graphene oxide in surfactant and graphene oxide solution is 1: 0.51: 5 or 1
: 1~1: 10.
3. preparation method according to claim 1, it is characterised in that: the graphene oxide ultrasound pretreated time is
10~60min, the rate of stirring are 100~600rad/min, and ultrasonic power is 150~1000W.
4. preparation method according to claim 1, it is characterised in that: cobalt salt described in step 1) is cobalt chloride, nitric acid
One of cobalt, cobalt acetate, cobaltous sulfate.
5. preparation method according to claim 1, it is characterised in that: in step 1), the cobalt salt and graphene oxide are molten
The mass ratio of graphene oxide in liquid is 10: 1~30: 1.
6. preparation method according to claim 1, it is characterised in that: in step 2), the quality of the precipitating reagent and cobalt salt
Than being 1: 0.1~1: 5.
7. preparation method according to claim 1, it is characterised in that: in step 2), the surfactant is poly- second
Any one of acrylamide PEI, PVAC polyvinylalcohol or polyvinylpyrrolidone PVP.
8. preparation method according to claim 1, it is characterised in that: when in step 3) using solvent heat, solvent is used
Dehydrated alcohol, dimethyl sulfoxide or n,N-Dimethylformamide.
9. preparation method according to claim 1, it is characterised in that: when the volume filling degree of water heating kettle in step 3) is
30%~90%, heating rate is 3~15 DEG C/min, and the reaction time is 8~16 hours.
10. preparation method according to claim 1, it is characterised in that: in step 4), obtained gel uses anhydrous second
Alcohol and water alternately washing 2~4 times, the temperature of freeze-drying are -120~-50 DEG C, and vacuum degree is at least 1 × 10-2Pa, freezing are dry
The dry time is 48~96 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710575852.7A CN109256279A (en) | 2017-07-14 | 2017-07-14 | A kind of graphene and Co3O4The preparation method of composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710575852.7A CN109256279A (en) | 2017-07-14 | 2017-07-14 | A kind of graphene and Co3O4The preparation method of composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109256279A true CN109256279A (en) | 2019-01-22 |
Family
ID=65051878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710575852.7A Pending CN109256279A (en) | 2017-07-14 | 2017-07-14 | A kind of graphene and Co3O4The preparation method of composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109256279A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710754A (en) * | 2020-05-11 | 2020-09-25 | 桂林理工大学 | Bi preparation by two-phase one-step solvothermal method2S3Method for preparing-graphene-ZnS photoelectric composite material |
| CN112951614A (en) * | 2021-02-26 | 2021-06-11 | 海南师范大学 | Cobaltosic oxide @ reticular biomass carbon composite material and preparation method and application thereof |
| CN113284740A (en) * | 2021-04-15 | 2021-08-20 | 上海应用技术大学 | Graphene oxide/MOF-derived porous cobalt oxide/graphene material and preparation and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941042A (en) * | 2012-10-25 | 2013-02-27 | 北京理工大学 | Graphene/metal oxide hybrid aerogel, preparation method and applications thereof |
| CN105161318A (en) * | 2015-07-07 | 2015-12-16 | 上海应用技术学院 | Three-dimensional graphite alkene/cobaltosic oxide composite material, preparation method thereof and application |
| CN105719849A (en) * | 2016-03-04 | 2016-06-29 | 上海应用技术学院 | Preparation method of shape-controlled graphene/Co(OH)2 composite materials |
| US20160218353A1 (en) * | 2013-09-09 | 2016-07-28 | Ajou University Industry-Academic Cooperation Foun Dation | Method for preparing metal oxide-graphene nanocomposite and method for preparing electrode using metal oxide-graphene nanocomposite |
-
2017
- 2017-07-14 CN CN201710575852.7A patent/CN109256279A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941042A (en) * | 2012-10-25 | 2013-02-27 | 北京理工大学 | Graphene/metal oxide hybrid aerogel, preparation method and applications thereof |
| US20160218353A1 (en) * | 2013-09-09 | 2016-07-28 | Ajou University Industry-Academic Cooperation Foun Dation | Method for preparing metal oxide-graphene nanocomposite and method for preparing electrode using metal oxide-graphene nanocomposite |
| CN105161318A (en) * | 2015-07-07 | 2015-12-16 | 上海应用技术学院 | Three-dimensional graphite alkene/cobaltosic oxide composite material, preparation method thereof and application |
| CN105719849A (en) * | 2016-03-04 | 2016-06-29 | 上海应用技术学院 | Preparation method of shape-controlled graphene/Co(OH)2 composite materials |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710754A (en) * | 2020-05-11 | 2020-09-25 | 桂林理工大学 | Bi preparation by two-phase one-step solvothermal method2S3Method for preparing-graphene-ZnS photoelectric composite material |
| CN112951614A (en) * | 2021-02-26 | 2021-06-11 | 海南师范大学 | Cobaltosic oxide @ reticular biomass carbon composite material and preparation method and application thereof |
| CN112951614B (en) * | 2021-02-26 | 2022-06-28 | 海南师范大学 | Cobaltosic oxide @ mesh biomass carbon composite material and preparation method and application thereof |
| CN113284740A (en) * | 2021-04-15 | 2021-08-20 | 上海应用技术大学 | Graphene oxide/MOF-derived porous cobalt oxide/graphene material and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106683905B (en) | A kind of preparation method of three nickel membrane electrode of porous nano curing | |
| CN105719849B (en) | A kind of graphene/Co (OH) of morphology controllable2The preparation method of composite material | |
| CN106315522B (en) | A kind of NiSe three-dimensional porous nano sheet materials and preparation method thereof for ultracapacitor | |
| CN103326007B (en) | The preparation method of three-dimensional graphite thiazolinyl tin dioxide composite material and application thereof | |
| CN108075128A (en) | A kind of N doping carbon coating cobalt nickel sulfide/graphene combination electrode material | |
| CN101982408A (en) | Graphene three-dimensional material as well as preparation method and application thereof | |
| CN106229503B (en) | A kind of preparation method of nickel oxide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery | |
| CN106057501B (en) | A kind of Ni (OH) for ultracapacitor2/ NiSe nano-bar materials and preparation method thereof | |
| CN106711419B (en) | The porous composite lithium ion battery cathode material of the NiO/C of core-shell structure copolymer shape | |
| CN109192535A (en) | A kind of preparation method of carbon based metal double-hydroxide electrode material for super capacitor | |
| CN109256279A (en) | A kind of graphene and Co3O4The preparation method of composite material | |
| CN106971855B (en) | A kind of nickel ferrite based magnetic loaded nanoparticle electrode material and preparation method and purposes | |
| CN104882298A (en) | Method for preparing NiCo2O4/graphene supercapacitor material with microwave method | |
| CN112670093A (en) | Porous Co3O4@ Ni-MOF core-shell structure nanosheet array material and preparation method and application thereof | |
| CN104143450A (en) | Method for preparing NiCo2O4 composite electrode material coated with conducting polymer | |
| CN106898503A (en) | A kind of cobalt acid nickel/cobalt sulfide nickel nano composite material of bar-shaped core shell structure, preparation method and applications | |
| CN104692468A (en) | Preparation method of three-dimensional multiwall hollow sphere NiO nano material | |
| CN107640761A (en) | The preparation method and stored energy application of graphene/carbon acid hydrogen nickel nanocube three-dimensional composite material | |
| CN106847530A (en) | A kind of nickel cobalt base-carbon nano tube combination electrode material and preparation method thereof | |
| CN105405675B (en) | A kind of Ag/Co (OH)2Nano-array film electrode material for super capacitor and preparation method thereof | |
| CN108899222A (en) | A kind of preparation method of electrode material for super capacitor | |
| CN110828193A (en) | Nano flower-shaped Ni-MOF material and preparation method and application thereof | |
| CN106328382A (en) | Carbon sphere / MoS2 composite material with yolk-shell structure and preparation method thereof | |
| CN108622946A (en) | Three-dimensional regular cube structure nano-nickel oxide and preparation method thereof and a kind of lithium battery | |
| CN105788881B (en) | A kind of preparation method of nitrogen doped corrugated carbon nanotube |
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: 20190122 |
|
| RJ01 | Rejection of invention patent application after publication |