CN106876170A - A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode - Google Patents
A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode Download PDFInfo
- Publication number
- CN106876170A CN106876170A CN201510930651.5A CN201510930651A CN106876170A CN 106876170 A CN106876170 A CN 106876170A CN 201510930651 A CN201510930651 A CN 201510930651A CN 106876170 A CN106876170 A CN 106876170A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- structural flexibility
- oxide
- hybrid structural
- 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
A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode, the present invention relates to the preparation method of combination electrode material.The invention solves the problems that existing chemical stripping method prepares Graphene is susceptible to stacking, it is impossible to the advantage of its huge specific surface area is played, while cobaltosic oxide has that cyclical stability is poor.Method：First, pretreated graphene oxide solution is prepared；2nd, three-dimensional structure Graphene/foam nickel material is prepared；3rd, cobalt acetate, hexa and three-dimensional structure Graphene/foam nickel material reaction, cleaning obtains cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode.The present invention is used for a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode.
Description
Technical field
The present invention relates to the preparation method of combination electrode material.
Background technology
With the emergence of the consumption electronic products such as increasing smart mobile phone, panel computer, portable reader, flexible energy storage device
Demand is growing day by day.In numerous flexible energy storage devices, ultracapacitor with its high power density, high workload efficiency, permanent service life with
And obtained extensive concern the features such as light pollution.At present, the exploitation of flexible super capacitor electrode material is faced with that specific capacitance value is relatively low, energy
The relatively low problem of metric density.Therefore, a kind of high specific capacitance is developed, the flexible electrode material of high-energy-density is the current focus studied.
Graphene is a kind of Novel Carbon Nanomaterials, with excellent electric conductivity, outstanding mechanical performance, chemical stability high, huge ratio
The advantages of surface area, extensive use is obtained in energy storage device.At present, the preparation method of common Graphene mainly prepares stone using chemical stripping method
Black alkene, its major advantage is low cost, can be prepared on a large scale.But Graphene is prepared using chemical stripping method and is susceptible to stacking, it is impossible to sent out
The advantage of its huge specific surface area is waved, and then causes that the specific capacitance value of prepared Graphene electrodes material is far below its theoretical value.
Cobaltosic oxide due to its larger theoretical specific capacitance value (3560F/g), environment-friendly, preferable chemical property, as ultracapacitor
Electrode material has obtained extensive concern.But in its charge and discharge process, cobaltosic oxide is susceptible to the expansion and contraction of volume, easily occur de-
Fall, influence its electrochemical stability, limit its application in practice.
The content of the invention
The invention solves the problems that existing chemical stripping method prepares Graphene is susceptible to stacking, it is impossible to the advantage of its huge specific surface area is played, while four oxygen
Change three cobalts and there is a problem of that cyclical stability is poor, and a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode is provided.
A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode, specifically follows the steps below：
First, rotating speed be 3000 revs/min~5000 revs/min under conditions of, by graphene oxide solution centrifugal treating 2min~10min after,
10min~30min is then sonicated, impurity screening obtains pretreated graphene oxide solution；
The concentration of described graphene oxide solution is 0.1mg/mL~1mg/mL；
2nd, 1., at room temperature, nickel foam is placed in reaction 1min~5min in pretreated graphene oxide solution, is then in temperature
3min~10min is dried in 50 DEG C~100 DEG C of vacuum drying chamber, material after being reacted；2., at room temperature, material after reaction is placed in
1min~5min is reacted in pretreated graphene oxide solution, is then dried in the vacuum drying chamber that temperature is 50 DEG C~100 DEG C
1min~5min；3., repeat step two 2. 2 times~9 times, obtain graphene oxide；4., by graphene oxide be placed in temperature for 50 DEG C~
3min~10min is dried in 200 DEG C of vacuum drying chamber, dried graphene oxide is obtained；5., it is in the atmosphere protections of H 2 and temperature
Under conditions of 200 DEG C~400 DEG C, dried graphene oxide is placed in chemical vapor deposition stove, thermal reduction 1h~3h obtains three-dimensional knot
Structure Graphene/foam nickel material；
3rd, the cobalt acetate aqueous solution and the hexa aqueous solution are mixed, is placed in stainless steel cauldron, then again by three-dimensional structure graphite
Alkene/foam nickel material is placed in stainless steel cauldron, closed reactor, will be closed after reactor be placed in the baking box that temperature is 50 DEG C~300 DEG C instead
1h~12h is answered, foam nickel material is obtained, after reaction terminates, foam nickel material is taken out, with distilled water flushing 3 times, that is, four oxidations three is obtained
Cobalt/Graphene three-dimensional hybrid structural flexibility electrode；Described cobalt acetate concentration of aqueous solution is 0.001 mol/L~0.01 mol/L；Institute
The hexa concentration of aqueous solution stated is 0.001 mol/L~0.01 mol/L；The described cobalt acetate aqueous solution and hexa-methylene four
The volume ratio of amine aqueous solution is 1:1.
The beneficial effects of the invention are as follows：
1st, present invention preparation three-dimensional structure Graphene method is simple, efficient, controllable, and three-dimensional structure Graphene replicates the three-dimensional framework of nickel foam
Structure, can be effectively prevented from the stack-up issue of Graphene, while being tightly combined between Graphene and nickel substrate, be effectively prevented from being led using binding agent
The problems such as causing compared with high contact resistance and poor cyclical stability.
2nd, the present invention synthesizes cobaltosic oxide using hydro-thermal method, using the specific capacitance value higher of cobaltosic oxide, will be combined by Graphene
Nanostructured cobaltosic oxide active material.The Graphene of three-dimensional structure both can greatly improve cobaltosic oxide relatively low as the substrate for carrying
Electrical conductivity, while its cyclical stability can be improved to meet actual demand.Graphene and cobaltosic oxide have excellent mechanical performance, can be with
Its specific capacitance value high and energy density and good cyclical stability are remained in that after multiple bend tension, this causes prepared combination electrode material
Material is expected to possess widely in flexible energy storage device field, can significantly improve the scarce of the relatively low specific capacitance value of graphene-based electrode and energy density
Point, meets its application in practice.
3rd, low cost of the present invention, method is simple, efficiency high, and cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode prepared by the present invention exists
Specific capacitance value in the KOH electrolyte of 1 mol/L under 0.2A/g current densities is up to 879F/g, and its energy density can reach 40Wh/kg, together
When the stretchable bending flexible electrode material that provides of the present invention, be expected to possess in flexible energy storage device field and be widely applied.
The present invention is used for a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, also including any combination between each specific embodiment.
Specific embodiment one：A kind of preparation method of the cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode described in present embodiment, tool
Body is followed the steps below：
First, under conditions of being 3000 revs/min~5000 revs/min in rotating speed, by graphene oxide solution centrifugal treating 2min~10min
Afterwards, 10min~30min is then sonicated, impurity screening obtains pretreated graphene oxide solution；
The concentration of described graphene oxide solution is 0.1mg/mL~1mg/mL；
3rd, 1., at room temperature, nickel foam is placed in reaction 1min~5min in pretreated graphene oxide solution, then in temperature
To dry 3min~10min in 50 DEG C~100 DEG C of vacuum drying chambers, after being reacted material 2., at room temperature, by material after reaction
Material is placed in reaction 1min~5min in pretreated graphene oxide solution, is then done in the vacuum drying chamber that temperature is 50 DEG C~100 DEG C
Dry 1min~5min；3., repeat step two 2. 2 times~9 times, obtain graphene oxide and 4., by graphene oxide be placed in temperature be
3min~10min is dried in 50 DEG C~200 DEG C of vacuum drying chamber, dried graphene oxide is obtained；5., protected in the atmosphere of H 2
Protect and temperature be under conditions of 200 DEG C~400 DEG C, dried graphene oxide to be placed in chemical vapor deposition stove, thermal reduction 1h~3h,
Obtain three-dimensional structure Graphene/foam nickel material；
3rd, the cobalt acetate aqueous solution and the hexa aqueous solution are mixed, is placed in stainless steel cauldron, then again by three-dimensional structure graphite
Alkene/foam nickel material is placed in stainless steel cauldron, closed reactor, will be closed after reactor be placed in the baking box that temperature is 50 DEG C~300 DEG C
Middle reaction 1h~12h, obtains foam nickel material, after reaction terminates, takes out foam nickel material, with distilled water flushing 3 times, that is, obtains four oxygen
Change three cobalts/Graphene three-dimensional hybrid structural flexibility electrode；
Described cobalt acetate concentration of aqueous solution is 0.001 mol/L~0.01 mol/L；Described hexa concentration of aqueous solution is
0.001 mol/L~0.01 mol/L；The described cobalt acetate aqueous solution and the volume ratio of the hexa aqueous solution are 1:1.
Specific embodiment two：
Present embodiment from unlike specific embodiment one：Step 2 1. described in nickel foam successively with watery hydrochloric acid be cleaned by ultrasonic 5min,
Acetone is cleaned by ultrasonic 5min and deionized water is cleaned by ultrasonic 5min.Other are identical with specific embodiment one.
Specific embodiment three：
Unlike one of present embodiment and specific embodiment one or two：Reactor after will be closed in step 3 be placed in temperature for 75 DEG C~
2h~7h is reacted in 210 DEG C of baking box, foam nickel material is obtained.Other are identical with specific embodiment one or two.
Specific embodiment four：
Unlike one of present embodiment and specific embodiment one to three：Cobalt acetate concentration of aqueous solution described in step 3 for 0.001 mole/
Rise~0.005 mol/L；Hexa concentration of aqueous solution described in step 3 is 0.001 mol/L~0.005 mol/L.Its
It is identical with specific embodiment one to three.
Claims (10)
1. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode, it is characterised in that a kind of cobalt oxide/graphene is three-dimensional
The preparation method of mixed structure flexible electrode is followed the steps below：
First, rotating speed be 3000 revs/min~5000 revs/min under conditions of, by graphene oxide solution centrifugal treating 2min~10min after,
10min~30min is then sonicated, impurity screening obtains pretreated graphene oxide solution；
The concentration of described graphene oxide solution is 0.1mg/mL~1mg/mL；
2nd, 1., at room temperature, nickel foam is placed in reaction 1min~5min in pretreated graphene oxide solution, is then in temperature
3min~10min is dried in 50 DEG C~100 DEG C of vacuum drying chamber, material after being reacted；2., at room temperature, material after reaction is placed in
1min~5min is reacted in pretreated graphene oxide solution, is then dried in the vacuum drying chamber that temperature is 50 DEG C~100 DEG C
1min~5min；3., repeat step two 2. 2 times~9 times, obtain graphene oxide；4., by graphene oxide be placed in temperature for 50 DEG C~
3min~10min is dried in 200 DEG C of vacuum drying chamber, dried graphene oxide is obtained；5., it is in H2 atmosphere protections and temperature
Under conditions of 200 DEG C~400 DEG C, dried graphene oxide is placed in chemical vapor deposition stove, thermal reduction 1h~3h obtains three-dimensional knot
Structure Graphene/foam nickel material；
3rd, the cobalt acetate aqueous solution and the hexa aqueous solution are mixed, is placed in stainless steel cauldron, then again by three-dimensional structure graphite
Alkene/foam nickel material is placed in stainless steel cauldron, closed reactor, will be closed after reactor be placed in the baking box that temperature is 50 DEG C~300 DEG C instead
1h~12h is answered, foam nickel material is obtained, after reaction terminates, foam nickel material is taken out, with distilled water flushing 3 times, that is, four oxidations three is obtained
Cobalt/Graphene three-dimensional hybrid structural flexibility electrode；Described cobalt acetate concentration of aqueous solution is 0.001 mol/L~0.01 mol/L；It is described
Hexa concentration of aqueous solution be 0.001 mol/L~0.01 mol/L；The described cobalt acetate aqueous solution and hexa water
The volume ratio of solution is 1:1.
2. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, it is characterised in that step
Rapid two 1. described in nickel foam be cleaned by ultrasonic 5min, acetone with watery hydrochloric acid successively and be cleaned by ultrasonic 5min and deionized water and be cleaned by ultrasonic 5min.
3. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, it is characterised in that step
Reactor after will be closed in rapid three is placed in reaction 2h~7h in the baking box that temperature is 75 DEG C~210 DEG C, obtains foam nickel material.
4. according to claim 1 a kind of four the preparation method of three/Graphene three-dimensional hybrid structural flexibility electrode is aoxidized, it is characterised in that step
Cobalt acetate concentration of aqueous solution described in three is 0.001 mol/L~0.005 mol/L；The hexa aqueous solution described in step 3
Concentration is 0.001 mol/L~0.005 mol/L.
5. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, it is characterised in that step
The concentration of the graphene oxide solution described in rapid is 0.1mg/mL~0.7mg/mL.
6. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, it is characterised in that step
The concentration of the graphene oxide solution described in rapid is 0.5mg/mL.
7. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, it is characterised in that step
Reactor after will be closed in rapid three is placed in reaction 1h~12h in the baking box that temperature is 150 DEG C, obtains foam nickel material.
8. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, it is characterised in that step
Reactor after will be closed in rapid three is placed in reaction 1h~12h in the baking box that temperature is 200 DEG C, obtains foam nickel material.
9. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, it is characterised in that step
Reactor after will be closed in rapid three is placed in the baking box that temperature is 150 DEG C and reacts 2h, obtains foam nickel material.
10. the preparation method of a kind of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, it is characterised in that
Cobalt acetate concentration of aqueous solution described in step 3 is 0.005 mol/L；Hexa concentration of aqueous solution described in step 3 is 0.002
Mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510930651.5A CN106876170A (en) | 2015-12-13 | 2015-12-13 | A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510930651.5A CN106876170A (en) | 2015-12-13 | 2015-12-13 | A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106876170A true CN106876170A (en) | 2017-06-20 |
Family
ID=59239026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510930651.5A Pending CN106876170A (en) | 2015-12-13 | 2015-12-13 | A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106876170A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110137430A (en) * | 2019-05-13 | 2019-08-16 | 上海大学 | The Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material and preparation method thereof |
-
2015
- 2015-12-13 CN CN201510930651.5A patent/CN106876170A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110137430A (en) * | 2019-05-13 | 2019-08-16 | 上海大学 | The Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105070526B (en) | A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode | |
| CN102064322B (en) | Silicon/graphene laminar composite material for lithium ion battery cathode and preparation method thereof | |
| CN110183718B (en) | Preparation method of three-dimensional porous double-crosslinked polyaniline/graphene composite xerogel | |
| CN106311282B (en) | A kind of porous monolayer 1T MoS2The preparation method and applications of nanometer sheet | |
| JP6599106B2 (en) | Negative electrode material for lithium secondary battery and method for producing the same, composition for negative electrode active material layer for lithium secondary battery using the negative electrode material, negative electrode for lithium secondary battery, and lithium secondary battery | |
| US20140113199A1 (en) | Nano-silicon composite lithium ion battery anode material coated with poly (3,4-ethylenedioxythiophene) as carbon source and preparation method thereof | |
| CN105060289A (en) | Method for preparing fewer-layer graphene on basis of biomass waste | |
| CN104810165B (en) | A kind of method for preparing nickel phosphide/Graphene composite thin film material | |
| CN107871876B (en) | Preparation method of bifunctional catalytic carbon material for zinc-air battery | |
| CN107161979B (en) | Carbon-based nanobelt porous material, and preparation method and application thereof | |
| Ra et al. | Synthesis of nitrogen doped graphite oxide and its electrochemical properties | |
| CN106784663A (en) | A kind of preparation method of the compound carbon cloth anode material of lithium-ion battery of antimony oxide | |
| CN116646501A (en) | Negative electrode slurry for sodium ion battery | |
| CN115010946B (en) | Metal-organic coordination polymer M 2 CA X Preparation method and application thereof | |
| CN109850886A (en) | A kind of cellular graphite material and the preparation method and application thereof | |
| CN107464934A (en) | One kind is based on graphene/carbon nano-tube combined conductive agent anode sizing agent preparation method | |
| CN109112565B (en) | Method for reducing charge transfer impedance of molybdenum disulfide-based catalytic hydrogen evolution electrode | |
| CN204333111U (en) | A kind of copper-base graphite alkene polymer lithium battery cathode structure | |
| CN105161690A (en) | Method for improving charge-discharge cycling capacity of molybdenum disulfide by doping graphene and titanium dioxide | |
| CN111541398A (en) | Preparation method of functionalized graphene roll-up photovoltaic PN junction | |
| CN103579626A (en) | Graphene/tin composite material, preparation method of grapheme/tin composite material, lithium ion battery and preparation method of lithium ion battery | |
| CN102951632A (en) | Preparation method of single-layer graphene oxide solution | |
| CN106876170A (en) | A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode | |
| CN106356203B (en) | A kind of cobalt acid nickel nano film/graphite felt composite material and its preparation and application | |
| CN107871616A (en) | A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170620 |