CN107871616A - 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
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- CN107871616A CN107871616A CN201610857261.4A CN201610857261A CN107871616A CN 107871616 A CN107871616 A CN 107871616A CN 201610857261 A CN201610857261 A CN 201610857261A CN 107871616 A CN107871616 A CN 107871616A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 22
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- 239000006260 foam Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 13
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 239000006261 foam material Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims 2
- 239000010439 graphite Substances 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- -1 oxygen Graphite alkene Chemical class 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 235000013495 cobalt Nutrition 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract description 18
- 239000007772 electrode material Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000004146 energy storage Methods 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- 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
- H01G11/24—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, 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
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- 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- 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
- H01G11/46—Metal oxides
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- 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
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- 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
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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.Graphene is prepared the invention solves existing chemical stripping method easily to stack, and can not play the advantage of its huge specific surface area, while cobaltosic oxide has the problem of cyclical stability difference.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, that is, 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, tablet personal computer, portable reader,
The demand of flexible energy storage device is growing day by day.In numerous flexible energy storage devices, ultracapacitor is with its high power density, senior engineer
The features such as making efficiency, permanent service life and light pollution has obtained extensive concern.At present, flexible super capacitor electrode material
The exploitation of material is faced with the problem of specific capacitance value is relatively low, energy density is relatively low.Therefore, a kind of high specific capacitance, high-energy are developed
The flexible electrode material of density is the focus studied at present.
Graphene is a kind of Novel Carbon Nanomaterials, has excellent electric conductivity, outstanding mechanical performance, high chemistry steady
The advantages that qualitative, huge specific surface area, extensive use is obtained in energy storage device.At present, the preparation side of common graphene
Method mainly prepares graphene using chemical stripping method, and its major advantage is that cost is low, can be prepared on a large scale.But use chemistry
Stripping method prepares graphene and easily stacked, and can not play the advantage of its huge specific surface area, and then cause prepared stone
The specific capacitance value of black alkene electrode material is far below its theoretical value.
Cobaltosic oxide is due to its larger theoretical specific capacitance value (3560F/g), environment-friendly, preferable electrochemistry
Can, obtain extensive concern as electrode material for super capacitor.But in its charge and discharge process, cobaltosic oxide is easily sent out
The expansion and contraction of raw body product, easily fall off, influence its electrochemical stability, limit its application in practice.
The content of the invention
Graphene is prepared the invention solves existing chemical stripping method easily to stack, and can not play its huge Large ratio surface
Long-pending advantage, while the problem of cyclical stability difference be present in cobaltosic oxide, and it is three-dimensional to provide a kind of cobalt oxide/graphene
The preparation method of mixed structure flexible electrode.
A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode, specifically according to following step
Suddenly carry out：
First, under conditions of rotating speed is 3000 revs/min~5000 revs/min, by graphene oxide solution centrifugal treating
After 2min~10min, 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,
Then 3min~10min, material after being reacted are dried in the vacuum drying chamber that temperature is 50 DEG C~100 DEG C；2., in room temperature
Under, material after reaction is placed in reaction 1min~5min in pretreated graphene oxide solution, is then 50 DEG C in temperature
1min~5min is dried in~100 DEG C of vacuum drying chamber；3., repeat step two 2. 2 times~9 times, obtain graphene oxide；
4., graphene oxide is placed in the vacuum drying chamber that temperature is 50 DEG C~200 DEG C and dries 3min~10min, after being dried
Graphene oxide；5., in H2Under conditions of atmosphere protection and temperature are 200 DEG C~400 DEG C, by dried graphene oxide
It is placed in chemical vapor deposition stove, heat-treats 1h~3h, obtain three-dimensional structure graphene/foam nickel material；
3rd, the cobalt acetate aqueous solution and the hexa aqueous solution are mixed, are placed in stainless steel cauldron, Ran Houzai
Three-dimensional structure graphene/foam nickel material is placed in stainless steel cauldron, closed reactor, will be closed after reactor be placed in
1h~12h is reacted in the baking box that temperature is 50 DEG C~300 DEG C, obtains foam nickel material, after reaction terminates, takes out nickel foam material
Material, with distilled water flushing 3 times, that is, obtain cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode；Described cobalt acetate water
Solution concentration is the mol/L of 0.001 mol/L~0.01；Described hexa concentration of aqueous solution be 0.001 mole/
Rise~0.01 mol/L；The described cobalt acetate aqueous solution and the volume ratio of the hexa aqueous solution are 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 bubble
The three dimensional skeletal structure of foam nickel, can be effectively prevented from the stack-up issue of graphene, while be combined between graphene and nickel substrate
Closely, the problems such as being effectively prevented from causing compared with high contact resistance and poor cyclical stability using binding agent.
2nd, the present invention, will be logical using the higher specific capacitance value of cobaltosic oxide using hydro-thermal method synthesis cobaltosic oxide
Cross the composite nanostructure cobaltosic oxide active material on graphene.Substrate of the graphene of three-dimensional structure as carrying, both
The relatively low electrical conductivity of cobaltosic oxide can greatly be improved, while its cyclical stability can be improved to meet actual need
Ask.Graphene and cobaltosic oxide have excellent mechanical performance, and its high ratio can be remained in that after multiple bend tension
Capacitance and energy density and good cyclical stability, this causes prepared combination electrode material to be expected in flexible accumulator
Part field possesses the shortcomings that widely, can significantly improving graphene-based electrode relatively low specific capacitance value and energy density, full
Its application in practice of foot.
3rd, cost of the present invention is low, and method is simple, efficiency high, cobalt oxide/graphene three-dimensional hybrid prepared by the present invention
Specific capacitance value of the structural flexibility electrode in the KOH electrolyte of 1 mol/L under 0.2A/g current densities is up to 879F/g, its
Energy density can reach 40Wh/kg, while stretchable bending flexible electrode material provided by the invention, be expected in flexible accumulator
Part field, which possesses, to be widely applied.
The present invention is used for a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode.
Embodiment
Technical solution of the present invention is not limited to the embodiment of act set forth below, in addition to each embodiment it
Between any combination.
Embodiment one：A kind of cobalt oxide/graphene three-dimensional hybrid structural flexibility described in present embodiment
The preparation method of electrode, is specifically followed the steps below：
First, under conditions of rotating speed is 3000 revs/min~5000 revs/min, by graphene oxide solution centrifugal treating
After 2min~10min, 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,
Then dry 3min~10min in temperature is 50 DEG C~100 DEG C of vacuum drying chamber, after being reacted material 2., in room temperature
Under, material after reaction is placed in reaction 1min~5min in pretreated graphene oxide solution, is then 50 DEG C in temperature
1min~5min is dried in~100 DEG C of vacuum drying chamber；3., repeat step two 2. 2 times~9 times, obtain graphene oxide；
4., graphene oxide is placed in the vacuum drying chamber that temperature is 50 DEG C~200 DEG C and dries 3min~10min, after being dried
Graphene oxide；5., in H2Under conditions of atmosphere protection and temperature are 200 DEG C~400 DEG C, by dried graphene oxide
It is placed in chemical vapor deposition stove, heat-treats 1h~3h, obtain three-dimensional structure graphene/foam nickel material；
3rd, the cobalt acetate aqueous solution and the hexa aqueous solution are mixed, are placed in stainless steel cauldron, Ran Houzai
Three-dimensional structure graphene/foam nickel material is placed in stainless steel cauldron, closed reactor, will be closed after reactor be placed in
1h~12h is reacted in the baking box that temperature is 50 DEG C~300 DEG C, obtains foam nickel material, after reaction terminates, takes out nickel foam material
Material, with distilled water flushing 3 times, that is, obtain cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode；
Described cobalt acetate concentration of aqueous solution is the mol/L of 0.001 mol/L~0.01；Described hexa
Concentration of aqueous solution is the mol/L of 0.001 mol/L~0.01；The described cobalt acetate aqueous solution and the hexa aqueous solution
Volume ratio be 1:1.
Embodiment two：
Present embodiment is unlike embodiment one：Step 2 1. described in nickel foam use watery hydrochloric acid successively
It is cleaned by ultrasonic 5min, acetone is cleaned by ultrasonic 5min and deionized water is cleaned by ultrasonic 5min.It is other identical with embodiment one.
Embodiment three：
Unlike one of present embodiment and embodiment one or two：Reactor after will be closed in step 3 is put
2h~7h is reacted in the baking box that temperature is 75 DEG C~210 DEG C, obtains foam nickel material.Other and embodiment one or two
It is identical.
Embodiment four：
Unlike one of present embodiment and embodiment one to three：The cobalt acetate aqueous solution described in step 3
Concentration is the mol/L of 0.001 mol/L~0.005；Hexa concentration of aqueous solution described in step 3 is 0.001
The mol/L of mol/L~0.005.It is other identical with embodiment one to three.
Claims (10)
- A kind of a kind of 1. preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode, it is characterised in that four oxygen The preparation method for changing three cobalts/graphene three-dimensional hybrid structural flexibility electrode follows the steps below：First, under conditions of rotating speed is 3000 revs/min~5000 revs/min, by graphene oxide solution centrifugal treating 2min After~10min, 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, then 3min~10min, material after being reacted are dried in the vacuum drying chamber that temperature is 50 DEG C~100 DEG C；2., at room temperature, Material after reaction is placed in pretreated graphene oxide solution reaction 1min~5min, then temperature be 50 DEG C~ 1min~5min is dried in 100 DEG C of vacuum drying chamber；3., repeat step two 2. 2 times~9 times, obtain graphene oxide；④、 Graphene oxide is placed in the vacuum drying chamber that temperature is 50 DEG C~200 DEG C and dries 3min~10min, obtains dried oxygen Graphite alkene；5., in H2Under conditions of atmosphere protection and temperature are 200 DEG C~400 DEG C, dried graphene oxide is placed in In chemical vapor deposition stove, 1h~3h is heat-treated, obtains three-dimensional structure graphene/foam nickel material；3rd, the cobalt acetate aqueous solution and the hexa aqueous solution are mixed, are placed in stainless steel cauldron, then again by three Dimension structure graphite alkene/foam nickel material is placed in stainless steel cauldron, closed reactor, will be closed after reactor be placed in temperature To react 1h~12h in 50 DEG C~300 DEG C of baking boxs, foam nickel material is obtained, after reaction terminates, foam nickel material is taken out, uses Distilled water flushing 3 times, that is, obtain cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode；The described cobalt acetate aqueous solution Concentration is the mol/L of 0.001 mol/L~0.01；Described hexa concentration of aqueous solution be 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.
- 2. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, It is characterized in that step 2 1. described in nickel foam be cleaned by ultrasonic 5min with watery hydrochloric acid successively, acetone is cleaned by ultrasonic and 5min and gone Ionized water is 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 characterized in that the reactor after will be closed in step 3, which is placed in the baking box that temperature is 75 DEG C~210 DEG C, reacts 2h~7h, obtain To foam nickel material.
- 4. a kind of preparation method of four oxidations, three/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, its It is characterised by cobalt acetate concentration of aqueous solution described in step 3 for the mol/L of 0.001 mol/L~0.005；Institute in step 3 The hexa concentration of aqueous solution stated is the mol/L of 0.001 mol/L~0.005.
- 5. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, It is characterized in that the concentration of the graphene oxide solution described in step 1 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 characterized in that the concentration of the graphene oxide solution described in step 1 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 characterized in that the reactor after will be closed in step 3, which is placed in the baking box that temperature is 150 DEG C, reacts 1h~12h, foam is obtained Nickel material.
- 8. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, It is characterized in that the reactor after will be closed in step 3, which is placed in the baking box that temperature is 200 DEG C, reacts 1h~12h, foam is obtained Nickel material.
- 9. a kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1, It is characterized in that the reactor after will be closed in step 3, which is placed in the baking box that temperature is 150 DEG C, reacts 2h, nickel foam material is obtained Material.
- A kind of 10. preparation side of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode according to claim 1 Method, it is characterised in that the cobalt acetate concentration of aqueous solution described in step 3 is 0.005 mol/L；Six described in step 3 are sub- Tetramine concentration of aqueous solution is 0.002 mol/L.
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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