CN110137430A - The Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material and preparation method thereof - Google Patents
The Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material and preparation method thereof Download PDFInfo
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- CN110137430A CN110137430A CN201910392056.9A CN201910392056A CN110137430A CN 110137430 A CN110137430 A CN 110137430A CN 201910392056 A CN201910392056 A CN 201910392056A CN 110137430 A CN110137430 A CN 110137430A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material and preparation method thereof, by infusion method, is loaded redox graphene, anneals under high temperature inert gas, prepare rGO/Ni foam composite material using nickel foam as carrier；Then electrochemical deposition method deposition Co (OH) is utilized2, prepare Co (OH)2/rGO/Ni foam；It is annealed again by Co (OH)2It is changed into Co3O4, finally obtain Co3O4/rGO/Ni foam.Combination electrode material of the present invention has good electrochemical cycle stability, porous array structure makes during as electrode material, improve the shuttle speed of electronics and ion, increase the contact area with electrolyte, to reach good electrochemical cycle stability, it can be used in energy storage equipment, improve electrochemical cycle stability.
Description
Technical field
The present invention relates to a kind of electrode materials and preparation method thereof, more particularly to a kind of transition metal nitride Metal Substrate
Combination electrode material and preparation method thereof is applied to energy storage material and facility technical field.
Background technique
Due to the fast development of material life, while material life is satisfied, people also start to pursue spiritual
It enjoys, such as to the higher pursuit of electronic product such as long-term standby and quick charge, so that with the quick update of mobile phone and plate
It regenerates, and comes in recent years, the self-driving travel to become more and more popular have stimulated the rapidly development of automobile industry.Due to being produced to electronics
Product it is long-term it is standby require so that more stringent requirements are proposed to the battery of product, in various energy storage devices, electrochemistry
The unique advantages such as safety non-pollution possessed by energy storage and energy storage transfer efficiency height, to become current solve the problems, such as
One of most suitable selection.Transistion metal compound includes transition metal nitride, transition metal oxide and transition
Other metallic compounds such as metal sulfide.Transistion metal compound is compared to carbon material, for alloy material, theoretical capacity
Height is a kind of negative electrode material for having the alternative graphite of prospect.It is wherein the most representative with transition metal oxide.Oxo transition metal
Compound includes CoOx,SnO2, NiO, VOxDeng, usually have times over conventional electrode materials theoretical capacity, be most to attract
One of alternative negative electrode material of power.Co3O4It is a kind of P-type semiconductor metal oxide, with Fe3O4It is similar, it can be seen as CoO
And Co2O3Complex.Co3O4As the negative electrode material of lithium ion battery, theoretical capacity is up to 890mAh g-1, and structure is steady
It is fixed, it is one of the selection as negative electrode material.But transistion metal compound and metal_based material carry out compound tense, transition metal
The phenomenon that there are unstable contacts between object and metal_based material is closed, while making transistion metal compound and metal_based material
Electric conductivity, electrochemical stability are also undesirable.
The bi-dimensional cellular shape structure that the structure of graphene is made of carbon hexatomic ring has ideal two dimensional crystal structure.
Because of its surface area height (2360m2g-1), the thickness of single-layer graphene can reach 0.34nm, and conductive characteristic is good, can make on a large scale
It is standby, it is considered to be nano material most thin at present.But it yet there are no and graphene is applied to transition metal combination electrode material
Relevant report.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material and preparation method thereof, the Co that the present invention uses3O4
It is a kind of transition metal oxide material, as the main constituents of composite material, so that the circulation for improving material is steady
Qualitative, grapheme material is a kind of material with conductive characteristic, and this material is easily prepared, and has fold, it is possible to provide big ratio
Surface area and good conductive characteristic, improve the electric conductivity of material.Nickel foam can serve as the support of material as substrate
Skeleton function, so that can be with the structure of stabilizing material during electrochemistry circulation.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material, using nickel foam as substrate,
And the support frame of the combination electrode material is served as, graphene layer has been loaded in nickel foam as buffer layer, in graphene
Co is combined on layer3O4Layer, makes Co using graphene layer3O4It is not directly contacted with nickel foam, being formed has three-dimensional porous array structure
Co3O4/ rGO/Ni foam combination electrode material.
A kind of Co of the three-dimensional porous array structure of the present invention3O4The preparation method of/rGO/Ni foam combination electrode material, packet
It includes following steps: using nickel foam as substrate, annealing, prepare by load graphene and at high temperature under inert gas shielding
RGO/Ni foam composite material recycles electrochemical deposition method and anneals at moderate temperatures, so that preparing has three-dimensional more
The Co of hole array structure3O4/ rGO/Ni foam combination electrode material.
As currently preferred technical solution, the Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material
The preparation method of material, includes the following steps:
Firstly, by infusion method, redox graphene is loaded using the nickel foam by pre-processing as carrier,
It anneals under high temperature inert gas, prepares rGO/Ni foam composite material；
Then, using electrochemical deposition method, in Co3O4Co (OH) is deposited on the basis of/rGO2Metal hydroxides film layer,
Prepare Co (OH)2/ rGO/Ni foam composite material；
Finally, using annealing process, by Co (OH)2Co (OH) in/rGO/Ni foam2It is changed into Co3O4, final to obtain
Co with three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material.
As currently preferred technical solution, for the temperature annealed not less than 600 DEG C, annealing time is no less than 2h.
The technical solution further preferred as the present invention, a kind of Co of three-dimensional porous array structure3O4/rGO/Ni foam
The preparation method of combination electrode material, includes the following steps:
A. rGO is synthesized:
2.5g potassium peroxydisulfate and at least 2.5g phosphorus pentoxide are weighed, adds at least 12mL concentrated sulfuric acid, after stirring and dissolving
It is added in 1~2 time hour again and is no less than 3.0g graphite powder, and constantly stirred；Then it is not higher than again in oil bath temperature
It is stirred to react at 80 DEG C at least 4.5 hours；Then it carries out after being cooled to room temperature, is added and is no less than the dilution of 500mL deionized water, stand
Supernatant liquor is outwelled after one evening, adding water cleaning to pH is 7, and graphite is dried for standby by filtering at not less than 60 DEG C；Then will
Graphite is finely ground, is slowly added in at least concentrated sulfuric acid of 120mL in batches, is then added under ice bath and is no less than the ground of 15g
Potassium permanganate reacts at least 2 hours at not higher than 35 DEG C, is then slowly added in the no less than deionized water of 250mL, stirs
After mixing at least 2 hours, at least 700mL deionized water is added, it is 30% that at least mass percent concentration of 20mL, which is slowly added dropwise,
H2O2Solution makes mixed solution become glassy yellow, and generates with a large amount of bubbles, outwells supernatant liquor after being then allowed to stand an evening；
It states then up and HCl solution that at least mass percent concentration of 100mL is 98% and at least is added in remaining bottom solution
900mL deionized water washes away metal ion using hydrochloric acid, constantly plus after water centrifugation, until pH is 7, the oxidation being in neutrality
Graphene solution, it is spare；
B. rGO/Ni foam is synthesized:
Nickel foam after peracid, acetone and ethanol washing is put in the graphene oxide prepared in the step a
In solution, so that foam nickel surface is adhered to graphene film, then take out nickel foam, by the nickel foam of deposition attachment graphene film in not
Lower than at least 2h that annealed in the inert gas shielding atmosphere at 600 DEG C, rGO/Ni foam intermediate materials are obtained, it is spare；
C. the Co of three-dimensional porous array structure is synthesized3O4/ rGO/Ni foam combination electrode material:
The rGO/Ni foam intermediate materials prepared in the step b are placed in three electrode assemblies, compound concentration is not low
In the Co (NO of 0.1M3)2Aqueous solution carries out electro-deposition in -1.4V~1.5V voltage range, makes rGO/Ni foam intermediate materials
Continue to deposit Co (OH) on graphene layer2, prepare Co (OH)2/ rGO/Ni foam material, then by Co (OH)2/rGO/Ni
Foam material is dried after taking out, and is made annealing treatment, is can be obtained with three-dimensional porous array at not less than 600 DEG C
The Co of structure3O4/ rGO/Ni foam combination electrode material.It is preferred that electro-deposition number is 1,2,4 or 8 time.It is preferred that make annealing treatment
Heating rate is 2~5 DEG C/min.It is preferred that carrying out electro-deposition in -0.4V~0.6V voltage range, make rGO/Ni foam intermediate wood
Continue to deposit Co (OH) on the graphene layer of material2, prepare Co (OH)2/ rGO/Ni foam material.
The present invention prepares rGO/Ni foam composite wood using nickel foam after treatment as substrate, by loading rGO
Material forms one layer of metal hydroxides (Co of deposition using electrochemical deposition method afterwards on the basis of rGO/Ni foam
(OH)2), prepare Co (OH)2/ rGO/Ni foam composite material finally selects heat treatment process appropriate by Co (OH)2Transformation
At Co3O4。
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the present invention has loaded graphene, in nickel foam by immersion process simple to operation so as to improve Co3O4
The electric conductivity of material, and by the graphene film with buffer function, so that the Co of growth on it3O4In electro-chemical test
When show good electrochemical stability；
2. the present invention is using graphene for Co3O4Stability have a good booster action, by being made with graphene
For buffer layer, to solve Co3O4Unstable contact between nickel foam.And this effect is so that Co3O4It can be fine
Ground is securely seated between on graphene film, to make Co3O4Show good chemical property；
3. the present invention is by using nickel foam as base load graphene and Co3O4, shown in electrochemistry fabulous
Stability, to demonstrate base foam nickel for Co3O4Electrochemical stability outstanding role；
4. present invention load graphene is not only the electric conductivity for improving material, and also and Co3O4Material is shown centainly
Synergistic effect, and it is this effect so that material under the premise of the electric discharge of larger current density, has still kept higher ratio
Capacity and cyclical stability.
Detailed description of the invention
Fig. 1 is the three-dimensional porous array structure Co of one method of embodiment of the present invention preparation3O4/ rGO/Ni foam combination electrode
The XRD diagram of material and Ni foam.
Fig. 2 is the three-dimensional porous array structure Co of one method of embodiment of the present invention preparation3O4/ rGO/Ni foam combination electrode
The peak position figure of redox graphene in material.
Fig. 3 is the three-dimensional porous array structure Co of one method of embodiment of the present invention preparation3O4/ rGO/Ni foam combination electrode
The x-ray photoelectron spectroscopy figure of material.
Fig. 4 is the three-dimensional porous array structure Co of one method of embodiment of the present invention preparation3O4/ rGO/Ni foam combination electrode
The SEM picture of material.
Fig. 5 is the three-dimensional porous array structure Co of one method of embodiment of the present invention preparation3O4/ rGO/Ni foam combination electrode
More times of cycle performance performance maps of material.
Fig. 6 is the three-dimensional porous array structure Co of one method of embodiment of the present invention preparation3O4/ rGO/Ni foam combination electrode
The haploidy energy cycle performance figure of material.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under:
Following embodiments meet following condition:
1) all glass apparatus used of QDs are prepared before experiment, in experimentation and rotor all need to be in the king newly prepared
It is impregnated two hours in the strong acid solution that water, i.e. concentrated hydrochloric acid and concentrated nitric acid volume ratio are 3:1, prepares QDs@SiO2All glass used
Glass instrument and rotor need to all impregnate two hours in the alkali cylinder newly prepared, and wherein the lye in alkali cylinder is sodium hydroxide and volume ratio
For the ethyl alcohol and ion water mixed liquid of 3:1.Then it is washed with deionized water, back-off is put into electric drying oven with forced convection, is then dried
It is stand-by after dry；
2) entire experimental water be all with the deionized water of the membrane filtration of 220nm, referred to as film water；Entire reaction exists
It is carried out under the conditions of 25 DEG C.The quality that guarantee prepares Silica-coated quantum dot is stablized.
Embodiment one:
In the present embodiment, a kind of Co of three-dimensional porous array structure3O4The preparation of/rGO/Ni foam combination electrode material
Method includes the following steps:
A. rGO is synthesized:
2.5g potassium peroxydisulfate and 2.5g phosphorus pentoxide are weighed, adds the 12mL concentrated sulfuric acid, after stirring and dissolving, then 1~2
3.0g graphite powder is added in a hour time, and constantly stirs；Then it is small that 4.5 are stirred to react at being again 80 DEG C in oil bath temperature
When；Then it carries out after being cooled to room temperature, the dilution of 500mL deionized water is added, outwells supernatant liquor after standing an evening, adds water cleaning
It is 7 to pH, graphite is dried for standby by filtering at 60 DEG C；Then graphite is finely ground, it is slowly added to the concentrated sulfuric acid of 120mL in batches
In, the ground potassium permanganate of 15g is then added under ice bath, reacts 2 hours, is then slowly added at 35 DEG C
In the deionized water of 250mL, after stirring 2 hours, 700mL deionized water is added, the mass percent that 20mL is slowly added dropwise is dense
The H that degree is 30%2O2Solution makes mixed solution become glassy yellow, and generates with a large amount of bubbles, outwells after being then allowed to stand an evening
Supernatant liquor；State then up in remaining bottom solution be added 100mL mass percent concentration be 98% HCl solution and
900mL deionized water washes away metal ion using hydrochloric acid, constantly plus after water centrifugation, until pH is 7, the oxidation being in neutrality
Graphene solution, it is spare；
B. rGO/Ni foam is synthesized:
Nickel foam is cut into disc-shaped by slicer, by the foam of the disc-shaped after peracid, acetone and ethanol washing
Nickel is put in the graphene oxide solution prepared in the step a, and foam nickel surface is made to adhere to graphene film, so that oxidation stone
Black alkene piece is attached on the skeleton of nickel foam, then takes out nickel foam, drying, by deposition attachment graphene film nickel foam in
Annealing 2h is carried out in inert gas shielding atmosphere at 600 DEG C, obtains rGO/Ni foam intermediate materials, it is spare；
C. the Co of three-dimensional porous array structure is synthesized3O4/ rGO/Ni foam combination electrode material:
The rGO/Ni foam intermediate materials prepared in the step b are placed in three electrode assemblies, compound concentration is
Co (the NO of 0.1M3)2Aqueous solution, and the rGO/Ni foam prepared is immersed into Co (NO3)2In aqueous solution, in -1.4V~1.5V
Voltage range carries out electro-deposition 1 using three electrodes and encloses, i.e., electro-deposition number is 1 time, makes the graphite of rGO/Ni foam intermediate materials
Continue to deposit Co (OH) on alkene layer2, prepare Co (OH)2/ rGO/Ni foam material, then by Co (OH)2/rGO/Ni foam
Material is dried after taking out, and annealing is carried out at 600 DEG C 2 hours, and the heating rate of annealing is 2 DEG C/min,
The Co with three-dimensional porous array structure can be obtained3O4/ rGO/Ni foam combination electrode material.
Experimental test and analysis:
To the Co3O4/rGO/Ni foam combination electrode material manufactured in the present embodiment with three-dimensional porous array structure into
Row electrochemical property test:
It prepares material and is tested by being assembled into half-cell, assembling flow path is to be placed in prepared electricity on negative electrode casing
After the material of pole, it is about 80 μ l that electrolyte, which is added dropwise, after be put into diaphragm, then identical electrolyte is added dropwise, then be respectively implanted lithium piece, iron
Piece, washer and anode cover are put into tablet press machine, pressed at half-cell.Multichannel battery instrument is put in be tested.The active matter of battery
Matter quality is the quality of nickel itself of defoaming, size of current=active material quality (mg) * multiplying power (A g-1)
The XRD of product is seen figure 1 and figure 2, and Fig. 1 is the three-dimensional porous array structure of one method of embodiment of the present invention preparation
Co3O4The XRD diagram of/rGO/Ni foam combination electrode material and redox graphene, the spectral line of lower section is NF spectral line in figure.Figure
The 2 three-dimensional porous array structure Co prepared for one method of the embodiment of the present invention3O4/ rGO/Ni foam combination electrode material and reduction
The peak position figure of graphene oxide, the spectral line of lower section is Ni foam spectral line in figure.
As seen from the figure, Co is contained in composite material manufactured in the present embodiment3O4, without obvious impurity peaks in the product.Fig. 3 is system
The XPS of standby composite material schemes, and figure a) is the total spectrogram of X-ray energy spectrum；Figure is b) X-ray spectrogram of cobalt element；Figure is c) carbon member
The X-ray spectrogram of element；Figure is d) X-ray spectrogram of oxygen element, from the figure 3, it may be seen that composite material manufactured in the present embodiment contains Co,
O, C element.Fig. 4 is the SEM figure of the composite material prepared, wherein scheming a) Co3O4Scanning of/rGO/Ni the foam under low resolution
Electron microscope；Scheme b) Co3O4The scanning electron microscope (SEM) photograph of/rGO/Ni foam at high resolutions, as can be seen from the figure material prepared
Array structure.Fig. 5 is the cycle performance figure of the electrode material for preparing under different current densities, as shown in Figure 5, Co3O4/
Cycle performance of lithium ion battery of the rGO/Ni foam electrode material under different current densities, in the electric current Jing Guo different multiplying
After the circulation of density, capacity is there is no largely changing, and when restoring to current density originally, capacity according to
It is old to may remain in original capacitance values or so.Fig. 6 is the cyclicity under single times of current density of the electrode material prepared
It can scheme, as seen from the figure Co3O4/ rGO/Ni foam is in 1.0A g-1Under lithium ion battery cycle performance, composite material pass through
After 200 loop tests, capacity retention ratio still can achieve 90% or more, and coulombic efficiency is not also decreased obviously, this
Show the Co of porous array structure3O4The electrochemical cycle stability of/rGO/Ni foam combination electrode material is good.
The Co of the three-dimensional porous array structure of the present embodiment3O4The preparation method of/rGO/Ni foam combination electrode material, belongs to
The field of energy electrode material.The main process of the method for the present invention and steps are as follows: firstly, with by the foam pre-processed
Nickel is loaded redox graphene, is annealed under high temperature inert gas, prepare rGO/Ni as carrier by infusion method
Foam composite material；Secondly, using electrochemical deposition method, in Co3O4Co (OH) is deposited on the basis of/rGO2Array prepares Co
(OH)2/rGO/Ni foam；Finally, selecting annealing temperature appropriate by Co (OH)2Co (OH) in/rGO/Ni foam2Transformation
For Co3O4, finally obtain Co3O4/rGO/Ni foam.Combination electrode material produced by the present invention is recycled with good electrochemistry
Stability.Co3O4It is a kind of transition metal oxide, there is high theoretical capacity.RGO as modification is a kind of by reduction
Graphene afterwards, this material have biggish surface area, can adequately contact with material, and good conductivity, Ke Yigai
The disadvantage of kind transition metal oxide electric conductivity deficiency.Prepared porous array structure, can make as electrode material
During, the shuttle speed of electronics and ion is improved, increases the contact area with electrolyte, to reach good electrochemistry
Cyclical stability.Composite material produced by the present invention can be used in energy storage equipment, improve energy storage equipment one
Long-term electrochemical cycle stability under constant current density.
Embodiment two:
The present embodiment is basically the same as the first embodiment, and is particular in that: annealing temperature heating rate is 5 DEG C/min
In the present embodiment, a kind of Co of three-dimensional porous array structure3O4The preparation of/rGO/Ni foam combination electrode material
Method includes the following steps:
A. rGO is synthesized:
2.5g potassium peroxydisulfate and 2.5g phosphorus pentoxide are weighed, adds the 12mL concentrated sulfuric acid, after stirring and dissolving, then 1~2
3.0g graphite powder is added in a hour time, and constantly stirs；Then it is small that 4.5 are stirred to react at being again 80 DEG C in oil bath temperature
When；Then it carries out after being cooled to room temperature, the dilution of 500mL deionized water is added, outwells supernatant liquor after standing an evening, adds water cleaning
It is 7 to pH, graphite is dried for standby by filtering at 60 DEG C；Then graphite is finely ground, it is slowly added to the concentrated sulfuric acid of 120mL in batches
In, the ground potassium permanganate of 15g is then added under ice bath, reacts 2 hours, is then slowly added at 35 DEG C
In the deionized water of 250mL, after stirring 2 hours, 700mL deionized water is added, the mass percent that 20mL is slowly added dropwise is dense
The H that degree is 30%2O2Solution makes mixed solution become glassy yellow, and generates with a large amount of bubbles, outwells after being then allowed to stand an evening
Supernatant liquor；State then up in remaining bottom solution be added 100mL mass percent concentration be 98% HCl solution and
900mL deionized water washes away metal ion using hydrochloric acid, constantly plus after water centrifugation, until pH is 7, the oxidation being in neutrality
Graphene solution, it is spare；
B. rGO/Ni foam is synthesized:
Nickel foam is cut into disc-shaped by slicer, by the foam of the disc-shaped after peracid, acetone and ethanol washing
Nickel is put in the graphene oxide solution prepared in the step a, and foam nickel surface is made to adhere to graphene film, so that oxidation stone
Black alkene piece is attached on the skeleton of nickel foam, then takes out nickel foam, drying, by deposition attachment graphene film nickel foam in
Annealing 2h is carried out in inert gas shielding atmosphere at 600 DEG C, obtains rGO/Ni foam intermediate materials, it is spare；
C. the Co of three-dimensional porous array structure is synthesized3O4/ rGO/Ni foam combination electrode material:
The rGO/Ni foam intermediate materials prepared in the step b are placed in three electrode assemblies, compound concentration is
Co (the NO of 0.1M3)2Aqueous solution, and the rGO/Ni foam prepared is immersed into Co (NO3)2In aqueous solution, in -1.4V~1.5V
Voltage range carries out electro-deposition 2 using three electrodes and encloses, i.e., electro-deposition number is 2 times, makes the graphite of rGO/Ni foam intermediate materials
Continue to deposit Co (OH) on alkene layer2, prepare Co (OH)2/ rGO/Ni foam material, then by Co (OH)2/rGO/Ni foam
Material is dried after taking out, and annealing is carried out at 600 DEG C 2 hours, and the heating rate of annealing is 5 DEG C/min,
The Co with three-dimensional porous array structure can be obtained3O4/ rGO/Ni foam combination electrode material.
Experimental test and analysis:
To the Co3O4/rGO/Ni foam combination electrode material manufactured in the present embodiment with three-dimensional porous array structure into
Row electrochemical property test:
It prepares material and is tested by being assembled into half-cell, assembling flow path is to be placed in prepared electricity on negative electrode casing
After the material of pole, it is about 80 μ l that electrolyte, which is added dropwise, after be put into diaphragm, then identical electrolyte is added dropwise, then be respectively implanted lithium piece, iron
Piece, washer and anode cover are put into tablet press machine, pressed at half-cell.Multichannel battery instrument is put in be tested.The active matter of battery
Matter quality is the quality of nickel itself of defoaming, size of current=active material quality (mg) * multiplying power (A g-1)
Contain Co in composite material manufactured in the present embodiment3O4, without obvious impurity peaks, prepared composite material in the product
Contain Co, O, C element, the array structure of material prepared.After the circulation of the current density of different multiplying, the present embodiment
The Co of the porous array structure of preparation3O4/ rGO/Ni foam combination electrode material capacity there is no largely changing, and
When restoring to current density originally, capacity still may remain in original capacitance values.It is manufactured in the present embodiment multiple
Condensation material is after 200 loop tests, and capacity retention ratio still can achieve 90% or more, and coulombic efficiency is not also bright
Aobvious decline, this shows the Co of porous array structure3O4The electrochemical cycle stability of/rGO/Ni foam combination electrode material
It is good.The present embodiment is annealed by load graphene and at high temperature under inert gas shielding, is prepared using nickel foam as substrate
RGO/Ni foam composite material recycles electrochemical deposition method and anneals at moderate temperatures, so that preparing has three-dimensional more
The Co of hole array structure3O4/ rGO/Ni foam combination electrode material.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that: electro-deposition number is 4 times.
In the present embodiment, a kind of Co of three-dimensional porous array structure3O4The preparation of/rGO/Ni foam combination electrode material
Method includes the following steps:
A. rGO is synthesized:
2.5g potassium peroxydisulfate and 2.5g phosphorus pentoxide are weighed, adds the 12mL concentrated sulfuric acid, after stirring and dissolving, then 1~2
3.0g graphite powder is added in a hour time, and constantly stirs；Then it is small that 4.5 are stirred to react at being again 80 DEG C in oil bath temperature
When；Then it carries out after being cooled to room temperature, the dilution of 500mL deionized water is added, outwells supernatant liquor after standing an evening, adds water cleaning
It is 7 to pH, graphite is dried for standby by filtering at 60 DEG C；Then graphite is finely ground, it is slowly added to the concentrated sulfuric acid of 120mL in batches
In, the ground potassium permanganate of 15g is then added under ice bath, reacts 2 hours, is then slowly added at 35 DEG C
In the deionized water of 250mL, after stirring 2 hours, 700mL deionized water is added, the mass percent that 20mL is slowly added dropwise is dense
The H that degree is 30%2O2Solution makes mixed solution become glassy yellow, and generates with a large amount of bubbles, outwells after being then allowed to stand an evening
Supernatant liquor；State then up in remaining bottom solution be added 100mL mass percent concentration be 98% HCl solution and
900mL deionized water washes away metal ion using hydrochloric acid, constantly plus after water centrifugation, until pH is 7, the oxidation being in neutrality
Graphene solution, it is spare；
B. rGO/Ni foam is synthesized:
Nickel foam is cut into disc-shaped by slicer, by the foam of the disc-shaped after peracid, acetone and ethanol washing
Nickel is put in the graphene oxide solution prepared in the step a, and foam nickel surface is made to adhere to graphene film, so that oxidation stone
Black alkene piece is attached on the skeleton of nickel foam, then takes out nickel foam, drying, by deposition attachment graphene film nickel foam in
Annealing 2h is carried out in inert gas shielding atmosphere at 600 DEG C, obtains rGO/Ni foam intermediate materials, it is spare；
C. the Co of three-dimensional porous array structure is synthesized3O4/ rGO/Ni foam combination electrode material:
The rGO/Ni foam intermediate materials prepared in the step b are placed in three electrode assemblies, compound concentration is
Co (the NO of 0.1M3)2Aqueous solution, and the rGO/Ni foam prepared is immersed into Co (NO3)2In aqueous solution, in -1.4V~1.5V
Voltage range carries out electro-deposition 4 using three electrodes and encloses, i.e., electro-deposition number is 4 times, makes the graphite of rGO/Ni foam intermediate materials
Continue to deposit Co (OH) on alkene layer2, prepare Co (OH)2/ rGO/Ni foam material, then by Co (OH)2/rGO/Ni foam
Material is dried after taking out, and annealing is carried out at 600 DEG C 2 hours, and the heating rate of annealing is 5 DEG C/min,
The Co with three-dimensional porous array structure can be obtained3O4/ rGO/Ni foam combination electrode material.
Experimental test and analysis:
To the Co3O4/rGO/Ni foam combination electrode material manufactured in the present embodiment with three-dimensional porous array structure into
Row electrochemical property test:
It prepares material and is tested by being assembled into half-cell, assembling flow path is to be placed in prepared electricity on negative electrode casing
After the material of pole, it is about 80 μ l that electrolyte, which is added dropwise, after be put into diaphragm, then identical electrolyte is added dropwise, then be respectively implanted lithium piece, iron
Piece, washer and anode cover are put into tablet press machine, pressed at half-cell.Multichannel battery instrument is put in be tested.The active matter of battery
Matter quality is the quality of nickel itself of defoaming, size of current=active material quality (mg) * multiplying power (A g-1)
Contain Co in composite material manufactured in the present embodiment3O4, without obvious impurity peaks, prepared composite material in the product
Contain Co, O, C element, the array structure of material prepared.After the circulation of the current density of different multiplying, the present embodiment
The Co of the porous array structure of preparation3O4/ rGO/Ni foam combination electrode material capacity there is no largely changing, and
When restoring to current density originally, capacity still may remain in original capacitance values.It is manufactured in the present embodiment multiple
Condensation material is after 200 loop tests, and capacity retention ratio still can achieve 90% or more, and coulombic efficiency is not also bright
Aobvious decline, this shows the Co of porous array structure3O4The electrochemical cycle stability of/rGO/Ni foam combination electrode material
It is good.The present embodiment is annealed by load graphene and at high temperature under inert gas shielding, is prepared using nickel foam as substrate
RGO/Ni foam composite material recycles electrochemical deposition method and anneals at moderate temperatures, so that preparing has three-dimensional more
The Co of hole array structure3O4/ rGO/Ni foam combination electrode material.
Example IV:
The present embodiment is substantially the same as in the previous example, and is particular in that: electro-deposition number is 8 times.
In the present embodiment, a kind of Co of three-dimensional porous array structure3O4The preparation of/rGO/Ni foam combination electrode material
Method includes the following steps:
A. rGO is synthesized:
2.5g potassium peroxydisulfate and 2.5g phosphorus pentoxide are weighed, adds the 12mL concentrated sulfuric acid, after stirring and dissolving, then 1~2
3.0g graphite powder is added in a hour time, and constantly stirs；Then it is small that 4.5 are stirred to react at being again 80 DEG C in oil bath temperature
When；Then it carries out after being cooled to room temperature, the dilution of 500mL deionized water is added, outwells supernatant liquor after standing an evening, adds water cleaning
It is 7 to pH, graphite is dried for standby by filtering at 60 DEG C；Then graphite is finely ground, it is slowly added to the concentrated sulfuric acid of 120mL in batches
In, the ground potassium permanganate of 15g is then added under ice bath, reacts 2 hours, is then slowly added at 35 DEG C
In the deionized water of 250mL, after stirring 2 hours, 700mL deionized water is added, the mass percent that 20mL is slowly added dropwise is dense
The H that degree is 30%2O2Solution makes mixed solution become glassy yellow, and generates with a large amount of bubbles, outwells after being then allowed to stand an evening
Supernatant liquor；State then up in remaining bottom solution be added 100mL mass percent concentration be 98% HCl solution and
900mL deionized water washes away metal ion using hydrochloric acid, constantly plus after water centrifugation, until pH is 7, the oxidation being in neutrality
Graphene solution, it is spare；
B. rGO/Ni foam is synthesized:
Nickel foam is cut into disc-shaped by slicer, by the foam of the disc-shaped after peracid, acetone and ethanol washing
Nickel is put in the graphene oxide solution prepared in the step a, and foam nickel surface is made to adhere to graphene film, so that oxidation stone
Black alkene piece is attached on the skeleton of nickel foam, then takes out nickel foam, drying, by deposition attachment graphene film nickel foam in
Annealing 2h is carried out in inert gas shielding atmosphere at 600 DEG C, obtains rGO/Ni foam intermediate materials, it is spare；
C. the Co of three-dimensional porous array structure is synthesized3O4/ rGO/Ni foam combination electrode material:
The rGO/Ni foam intermediate materials prepared in the step b are placed in three electrode assemblies, compound concentration is
Co (the NO of 0.1M3)2Aqueous solution, and the rGO/Ni foam prepared is immersed into Co (NO3)2In aqueous solution, in -1.4V~1.5V
Voltage range carries out electro-deposition 8 using three electrodes and encloses, i.e., electro-deposition number is 8 times, makes the graphite of rGO/Ni foam intermediate materials
Continue to deposit Co (OH) on alkene layer2, prepare Co (OH)2/ rGO/Ni foam material, then by Co (OH)2/rGO/Ni foam
Material is dried after taking out, and annealing is carried out at 600 DEG C 2 hours, and the heating rate of annealing is 2 DEG C/min,
The Co with three-dimensional porous array structure can be obtained3O4/ rGO/Ni foam combination electrode material.
Experimental test and analysis:
To the Co3O4/rGO/Ni foam combination electrode material manufactured in the present embodiment with three-dimensional porous array structure into
Row electrochemical property test:
It prepares material and is tested by being assembled into half-cell, assembling flow path is to be placed in prepared electricity on negative electrode casing
After the material of pole, it is about 80 μ l that electrolyte, which is added dropwise, after be put into diaphragm, then identical electrolyte is added dropwise, then be respectively implanted lithium piece, iron
Piece, washer and anode cover are put into tablet press machine, pressed at half-cell.Multichannel battery instrument is put in be tested.The active matter of battery
Matter quality is the quality of nickel itself of defoaming, size of current=active material quality (mg) * multiplying power (A g-1)
Contain Co in composite material manufactured in the present embodiment3O4, without obvious impurity peaks, prepared composite material in the product
Contain Co, O, C element, the array structure of material prepared.After the circulation of the current density of different multiplying, the present embodiment
The Co of the porous array structure of preparation3O4/ rGO/Ni foam combination electrode material capacity there is no largely changing, and
When restoring to current density originally, capacity still may remain in original capacitance values.It is manufactured in the present embodiment multiple
Condensation material is after 200 loop tests, and capacity retention ratio still can achieve 90% or more, and coulombic efficiency is not also bright
Aobvious decline, this shows the Co of porous array structure3O4The electrochemical cycle stability of/rGO/Ni foam combination electrode material
It is good.The present embodiment is annealed by load graphene and at high temperature under inert gas shielding, is prepared using nickel foam as substrate
RGO/Ni foam composite material recycles electrochemical deposition method and anneals at moderate temperatures, so that preparing has three-dimensional more
The Co of hole array structure3O4/ rGO/Ni foam combination electrode material.
Embodiment five:
The present embodiment is substantially the same as in the previous example, and is particular in that: the voltage range of electro-deposition be -0.4~
0.6V。
In the present embodiment, a kind of Co of three-dimensional porous array structure3O4The preparation of/rGO/Ni foam combination electrode material
Method includes the following steps:
A. rGO is synthesized:
2.5g potassium peroxydisulfate and 2.5g phosphorus pentoxide are weighed, adds the 12mL concentrated sulfuric acid, after stirring and dissolving, then 1~2
3.0g graphite powder is added in a hour time, and constantly stirs；Then it is small that 4.5 are stirred to react at being again 80 DEG C in oil bath temperature
When；Then it carries out after being cooled to room temperature, the dilution of 500mL deionized water is added, outwells supernatant liquor after standing an evening, adds water cleaning
It is 7 to pH, graphite is dried for standby by filtering at 60 DEG C；Then graphite is finely ground, it is slowly added to the concentrated sulfuric acid of 120mL in batches
In, the ground potassium permanganate of 15g is then added under ice bath, reacts 2 hours, is then slowly added at 35 DEG C
In the deionized water of 250mL, after stirring 2 hours, 700mL deionized water is added, the mass percent that 20mL is slowly added dropwise is dense
The H that degree is 30%2O2Solution makes mixed solution become glassy yellow, and generates with a large amount of bubbles, outwells after being then allowed to stand an evening
Supernatant liquor；State then up in remaining bottom solution be added 100mL mass percent concentration be 98% HCl solution and
900mL deionized water washes away metal ion using hydrochloric acid, constantly plus after water centrifugation, until pH is 7, the oxidation being in neutrality
Graphene solution, it is spare；
B. rGO/Ni foam is synthesized:
Nickel foam is cut into disc-shaped by slicer, by the foam of the disc-shaped after peracid, acetone and ethanol washing
Nickel is put in the graphene oxide solution prepared in the step a, and foam nickel surface is made to adhere to graphene film, so that oxidation stone
Black alkene piece is attached on the skeleton of nickel foam, then takes out nickel foam, drying, by deposition attachment graphene film nickel foam in
Annealing 2h is carried out in inert gas shielding atmosphere at 600 DEG C, obtains rGO/Ni foam intermediate materials, it is spare；
C. the Co of three-dimensional porous array structure is synthesized3O4/ rGO/Ni foam combination electrode material:
The rGO/Ni foam intermediate materials prepared in the step b are placed in three electrode assemblies, compound concentration is
Co (the NO of 0.1M3)2Aqueous solution, and the rGO/Ni foam prepared is immersed into Co (NO3)2In aqueous solution, in -0.4V~0.6V
Voltage range carries out electro-deposition 4 using three electrodes and encloses, i.e., electro-deposition number is 4 times, makes the graphite of rGO/Ni foam intermediate materials
Continue to deposit Co (OH) on alkene layer2, prepare Co (OH)2/ rGO/Ni foam material, then by Co (OH)2/rGO/Ni foam
Material is dried after taking out, and annealing is carried out at 600 DEG C 2 hours, and the heating rate of annealing is 5 DEG C/min,
The Co with three-dimensional porous array structure can be obtained3O4/ rGO/Ni foam combination electrode material.
Experimental test and analysis:
To the Co3O4/rGO/Ni foam combination electrode material manufactured in the present embodiment with three-dimensional porous array structure into
Row electrochemical property test:
It prepares material and is tested by being assembled into half-cell, assembling flow path is to be placed in prepared electricity on negative electrode casing
After the material of pole, it is about 80 μ l that electrolyte, which is added dropwise, after be put into diaphragm, then identical electrolyte is added dropwise, then be respectively implanted lithium piece, iron
Piece, washer and anode cover are put into tablet press machine, pressed at half-cell.Multichannel battery instrument is put in be tested.The active matter of battery
Matter quality is the quality of nickel itself of defoaming, size of current=active material quality (mg) * multiplying power (A g-1)
Contain Co in composite material manufactured in the present embodiment3O4, without obvious impurity peaks, prepared composite material in the product
Contain Co, O, C element, the array structure of material prepared.After the circulation of the current density of different multiplying, the present embodiment
The Co of the porous array structure of preparation3O4/ rGO/Ni foam combination electrode material capacity there is no largely changing, and
When restoring to current density originally, capacity still may remain in original capacitance values.It is manufactured in the present embodiment multiple
Condensation material is after 200 loop tests, and capacity retention ratio still can achieve 90% or more, and coulombic efficiency is not also bright
Aobvious decline, this shows the Co of porous array structure3O4The electrochemical cycle stability of/rGO/Ni foam combination electrode material
It is good.The Co of three-dimensional porous array structure is prepared in the present embodiment3O4/ rGO/Ni foam combination electrode material, is made with nickel foam
For substrate, and the support frame of the combination electrode material is served as, graphene layer has been loaded in nickel foam as buffer layer,
Co is combined on graphene layer3O4Layer, makes Co using graphene layer3O4It is not directly contacted with nickel foam, being formed has three-dimensional porous battle array
The Co of array structure3O4/ rGO/Ni foam combination electrode material.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
Without departing from the Co of the three-dimensional porous array structure of the present invention3O4/ rGO/Ni foam combination electrode material and preparation method thereof
Technical principle and inventive concept, belong to protection scope of the present invention.
Claims (8)
1. a kind of Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material, it is characterised in that: with nickel foam
As substrate, and the support frame of the combination electrode material is served as, graphene layer has been loaded in nickel foam as buffer layer,
Co is combined on graphene layer3O4Layer, makes Co using graphene layer3O4It is not directly contacted with, is formed with three-dimensional porous with nickel foam
The Co of array structure3O4/ rGO/Ni foam combination electrode material.
2. the Co of three-dimensional porous array structure described in a kind of claim 13O4The preparation side of/rGO/Ni foam combination electrode material
Method, which comprises the steps of: using nickel foam as substrate, by loading graphene and at high temperature inert gas
The lower annealing of protection, prepares rGO/Ni foam composite material, recycles electrochemical deposition method and anneal at moderate temperatures, from
And prepare the Co with three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material.
3. the Co of three-dimensional porous array structure according to claim 23O4The preparation side of/rGO/Ni foam combination electrode material
Method, which comprises the steps of:
Firstly, by infusion method, redox graphene is loaded, in height using the nickel foam by pre-processing as carrier
It anneals under warm inert gas, prepares rGO/Ni foam composite material；
Then, using electrochemical deposition method, in Co3O4Co (OH) is deposited on the basis of/rGO2Metal hydroxides film layer, preparation
Co (OH) out2/ rGO/Ni foam composite material；
Finally, using annealing process, by Co (OH)2Co (OH) in/rGO/Ni foam2It is changed into Co3O4, finally had
The Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material.
4. the Co of three-dimensional porous array structure according to Claims 2 or 33O4The system of/rGO/Ni foam combination electrode material
Preparation Method, which is characterized in that the temperature annealed is not less than 600 DEG C, and annealing time is no less than 2h.
5. the Co of three-dimensional porous array structure according to Claims 2 or 33O4The system of/rGO/Ni foam combination electrode material
Preparation Method, which comprises the steps of:
A. rGO is synthesized:
2.5g potassium peroxydisulfate and at least 2.5g phosphorus pentoxide are weighed, adds at least 12mL concentrated sulfuric acid, again 1 after stirring and dissolving
It is added in~2 times hour and is no less than 3.0g graphite powder, and constantly stirred；Then again in the case where oil bath temperature is not higher than 80 DEG C
It is stirred to react at least 4.5 hours；Then it carries out after being cooled to room temperature, is added and is no less than the dilution of 500mL deionized water, after standing an evening
Supernatant liquor is outwelled, adding water cleaning to pH is 7, and graphite is dried for standby by filtering at not less than 60 DEG C；Then graphite is ground
Carefully, it is slowly added in batches in at least concentrated sulfuric acid of 120mL, the ground permanganic acid for being no less than 15g is then added under ice bath
Potassium is reacted at least 2 hours at not higher than 35 DEG C, is then slowly added in the no less than deionized water of 250mL, and stirring is at least
After 2 hours, at least 700mL deionized water is added, the H that at least mass percent concentration of 20mL is 30% is slowly added dropwise2O2It is molten
Liquid makes mixed solution become glassy yellow, and generates with a large amount of bubbles, outwells supernatant liquor after being then allowed to stand an evening；Then to
The HCl solution and at least 900mL is gone that at least the mass percent concentration of 100mL is 98% are added in above-mentioned remaining bottom solution
Ionized water washes away metal ion using hydrochloric acid, and constantly plus after water centrifugation, until pH is 7, the graphene oxide being in neutrality is molten
Liquid, it is spare；
B. rGO/Ni foam is synthesized:
Will be through peracid, the nickel foam after acetone and ethanol washing is put in the graphene oxide solution prepared in the step a
In, so that foam nickel surface is adhered to graphene film, then take out nickel foam, by the nickel foam of deposition attachment graphene film in being not less than
Annealed at least 2h in inert gas shielding atmosphere at 600 DEG C, obtains rGO/Ni foam intermediate materials, spare；
C. the Co of three-dimensional porous array structure is synthesized3O4/ rGO/Ni foam combination electrode material:
The rGO/Ni foam intermediate materials prepared in the step b are placed in three electrode assemblies, compound concentration is not less than
Co (the NO of 0.1M3)2Aqueous solution carries out electro-deposition in the V voltage range of -1.4V~1.5, makes rGO/Ni foam intermediate materials
Continue to deposit Co (OH) on graphene layer2, prepare Co (OH)2/ rGO/Ni foam material, then by Co (OH)2/rGO/Ni
Foam material is dried after taking out, and is made annealing treatment, is can be obtained with three-dimensional porous array at not less than 600 DEG C
The Co of structure3O4/ rGO/Ni foam combination electrode material.
6. the Co of three-dimensional porous array structure according to claim 53O4The preparation side of/rGO/Ni foam combination electrode material
Method, it is characterised in that: in the step c, electro-deposition number is 1,2,4 or 8 time.
7. the Co of three-dimensional porous array structure according to claim 53O4The preparation side of/rGO/Ni foam combination electrode material
Method, it is characterised in that: the heating rate of annealing is 2~5 DEG C/min.
8. the Co of three-dimensional porous array structure according to claim 53O4The preparation side of/rGO/Ni foam combination electrode material
Method, it is characterised in that: carry out electro-deposition -0.4 to 0.6V voltage range, make the graphene layer of rGO/Ni foam intermediate materials
On continue deposit Co (OH)2, prepare Co (OH)2/ rGO/Ni foam material.
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| CN111624242A (en) * | 2020-04-23 | 2020-09-04 | 同济大学 | Preparation method of carbon-foam copper material and method for detecting formaldehyde in environmental water by using carbon-foam copper material as working electrode |
| CN112093856A (en) * | 2020-07-31 | 2020-12-18 | 同济大学 | Single-metal integrated electrode with convertible oxidation state copper and preparation method and application method thereof |
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Application publication date: 20190816 |