CN107967998A - The preparation method of grapheme foam nickel electrode - Google Patents
The preparation method of grapheme foam nickel electrode Download PDFInfo
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- CN107967998A CN107967998A CN201711174424.XA CN201711174424A CN107967998A CN 107967998 A CN107967998 A CN 107967998A CN 201711174424 A CN201711174424 A CN 201711174424A CN 107967998 A CN107967998 A CN 107967998A
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- nickel electrode
- foam nickel
- graphene oxide
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 82
- 239000006260 foam Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000007853 buffer solution Substances 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- IVLXQGJVBGMLRR-UHFFFAOYSA-N 2-aminoacetic acid;hydron;chloride Chemical compound Cl.NCC(O)=O IVLXQGJVBGMLRR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960001269 glycine hydrochloride Drugs 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 3
- -1 graphite alkene Chemical class 0.000 claims description 3
- 230000002000 scavenging effect Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004471 Glycine Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229960002449 glycine Drugs 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000033116 oxidation-reduction process Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000001680 brushing effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000931705 Cicada Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- 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
- 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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- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based 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
- Y02E60/10—Energy storage using batteries
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention relates to a kind of preparation method and applications of grapheme foam nickel electrode.Preparation method be nickel foam is cleaned, it is dry after be used as working electrode, in graphene oxide dispersion, utilize the obtained graphene oxide foam nickel electrode of cyclic voltammetry scanning, after drying, in glycine hydrochloride buffer solution, constant potential reduction is carried out, obtains grapheme foam nickel electrode.The preparation method of grapheme foam nickel electrode of the present invention, relative to the preparation method of other Graphene electrodes, the method for the present invention raw material is cheap, pollution-free, environmentally protective, easy to largely produce.The grapheme foam nickel electrode supported by nickel foam shows good capacitive property in neutral electrolyte, can be used for energy storage field.
Description
Technical field
The invention belongs to supercapacitor technologies field, and in particular to a kind of preparation method of grapheme foam nickel electrode and
It is applied.
Background technology
Graphene is by carbon atom sp2The honeycomb fashion net structure that hydridization is formed, there is monoatomic layer thickness to be for it
A kind of very thin two-dimensional structure material.Its theoretical specific surface area value is very high.Since graphene is possessed in light, heat, electricity etc.
Special nature, such as there is higher specific surface area and excellent electrical conductivity so that graphene ultracapacitor, battery etc. just
Face has wide application space.
It is many to prepare graphene method, including mechanical stripping method, chemical vapour deposition technique (Chemical Vapor
Deposition, CVD), oxidation-reduction method, solvent stripping method, solvent-thermal method etc..Mechanical stripping method is directly that graphene is thin
Piece is cut down from larger crystal；It is biochemical that chemical vapour deposition technique (CVD) refers to that reactive material is issued in gaseous condition
Reaction, generation solid matter are deposited on the solid matrix surface of heating, and then the technology of solid material is made.One kind is with nickel
For the simple cvd furnace of tubulose of substrate, carbonaceous gas is passed through, such as：Hydrocarbon, it resolves into carbon atom deposition at high temperature
On the surface of nickel, graphene is formed, by slight chemical etching, makes graphene film and the isolated graphene of nickel sheet thin
Film；Oxidation-reduction method refers to native graphite and the reaction of strong acid and oxidizing species generating graphite oxide (GO), by ultrasound
It is scattered to be prepared into graphene oxide (mono-layer graphite oxide), add the oxy radical that reducing agent removes graphite oxide surface, such as carboxylic
Base, epoxy group and hydroxyl, obtain graphene；The shortcomings that oxidation-reduction method is that magnanimity preparation easily brings waste liquor contamination and preparation
Graphene there are it is certain the defects of, cause graphene part electrical property loss of energy, be restricted the application of graphene；It is molten
The principle of agent stripping method be by a small amount of graphite dispersion in solvent, form the dispersion liquid of low concentration, utilize the effect of ultrasonic wave
The Van der Waals force of graphite layers is destroyed, solvent may be inserted into graphite layers at this time, is peeled off layer by layer, prepares graphene.This
Method will not destroy the structure of graphene as oxidation-reduction method, can prepare the graphene of high quality, shortcoming be yield very
It is low；Solvent-thermal method refers in special closed reactor (autoclave), using organic solvent as reaction medium, by by instead
System is answered to be heated to critical-temperature (or close to critical-temperature), itself produces high pressure and carries out material preparation in the reaction system
A kind of effective ways, solvent-thermal method solve the problems, such as prepare with scale graphene, while also bring very low negative of electrical conductivity
Face is rung.The material of graphene is very different, how to be prepared using graphene and produces the higher graphene electricity of quality in batches
Pole is still a problem.
Existing Graphene electrodes have is made film using technologies such as high vacuum, high pressure, plasmas, some films also need to
Substrate departs from, complex steps, complex process, and energy consumption is high, is not suitable for producing in batches；In addition, also having will be brushed using brushing method
Liquid is brushed in nickel foam, easily occur in brushing liquid painting process brushing liquid covering it is uneven, also need to be dried afterwards,
And need to be repeated a number of times, it is complicated, it is final to obtain the defects of product quality is not very stable.
The content of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of preparation method of grapheme foam nickel electrode.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include：
A kind of preparation method of grapheme foam nickel electrode, nickel foam is cleaned, it is dry after as working electrode, aoxidizing
In graphene dispersing solution, scanned using cyclic voltammetry and graphene oxide foam nickel electrode is made, after dry, in glycine-salt
In acid buffering solution, constant potential reduction is carried out, obtains grapheme foam nickel electrode.
The preparation method of grapheme foam nickel electrode as described above, it is preferable that the cleaning is to use deionization successively
Water, dilute hydrochloric acid, absolute ethyl alcohol, acetone are respectively washed.Further, nickel foam can be cleaned by ultrasonic using above-mentioned solution,
Each 3~50min of scavenging period.The frequency range of ultrasound is 50~100kHz.
The preparation method of grapheme foam nickel electrode as described above, it is preferable that the mass fraction of the dilute hydrochloric acid for 1~
5%.
The preparation method of grapheme foam nickel electrode as described above, it is preferable that after the cleaning it is dry use temperature for
60~110 DEG C, dry 10~60min, it is highly preferred that using vacuum drying.
The preparation method of grapheme foam nickel electrode as described above, it is preferable that oxygen in the graphene oxide dispersion
The mass concentration of graphite alkene is 2~4g/L.
The preparation method of grapheme foam nickel electrode as described above, it is preferable that the condition of the cyclic voltammetry be with
Saturated calomel electrode is reference electrode, and for platinized platinum to be -1.4~0.6V to electrode, voltage, it is to be scanned under 5~80mV/s to sweep speed.It is excellent
Choosing scanning 30-150 circle effects are preferable.
The preparation method of grapheme foam nickel electrode as described above, it is preferable that the graphene oxide nickel foam electricity
The drying of pole uses 80~115 DEG C of temperature, and vacuum condition drying, drying time is 10~60min.
The preparation method of grapheme foam nickel electrode as described above, it is preferable that the glycine hydrochloride buffer solution
The scope of pH value is 3~5, and the concentration of the glycine is 0.03mol L-1~0.2mol L-1。
The preparation method of grapheme foam nickel electrode as described above, it is preferable that the voltage of the constant potential reduction for-
1.6~-0.8V, 15~120min of recovery time.
Grapheme foam nickel electrode prepared by method as described above ultracapacitor, lithium ion battery, fuel cell and
Application in biology sensor.
(3) beneficial effect
The beneficial effects of the invention are as follows：
The preparation method of the grapheme foam nickel electrode of the present invention, compared with other Graphene electrodes preparation methods, uses
The mode of cyclic voltammetry scan and constant potential reduction hierarchical composition, with less raw material, processing step, easier operation side
Formula obtains the grapheme foam electrode of high capacitance performance.The preparation method of the present invention has the raw material used cheap, and pollution is small, behaviour
Make it is easy, it is environmentally protective, the advantages of easy to largely produce.And can be by varying cyclic voltammetry scan time, speed, permanent electricity
Position voltage, adjusts the performance of Graphene electrodes.The grapheme foam nickel electrode quality of preparation is good, has a small amount of oxygen-containing functional group,
Be conducive to increase the avtive spot of ion exchange, improve the capacitive property of Graphene electrodes.
The method of the present invention solves Graphene electrodes in the energy storage device application process such as ultracapacitor, and production technology is multiple
Miscellaneous, the problems such as energy consumption is big, product is unstable.The present invention realizes the batch production of the Graphene electrodes of nickel foam Auxiliary support, letter
Change flow, improve specific capacitance.The grapheme foam nickel electrode supported by nickel foam prepared is shown in neutral electrolyte
Good capacitive property, can be used for energy storage field.Specifically, the grapheme foam nickel electrode of preparation can be used for super capacitor
The fields such as device, lithium ion battery, fuel cell, biology sensor.The grapheme foam nickel electrode can also occur with lithium ion
Reaction, is conducive to induce the insertion of lithium ion, is applied to the cathode of lithium primary cell, avoids and made in the past with graphite oxide
It is toxic when hygroscopic property and fluorographite during electrode material are as electrode material.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of grapheme foam nickel electrode prepared by embodiment 1；
Fig. 2 is the Raman spectrogram of grapheme foam nickel electrode prepared by embodiment 1；
Fig. 3 is the XPS spectrum figure of grapheme foam nickel electrode prepared by embodiment 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of grapheme foam nickel electrode prepared by embodiment 1；
The energy density for the ultracapacitor that Fig. 5 is prepared for grapheme foam nickel electrode prepared by embodiment 1, power are close
Degree；
Fig. 6 is the charging and discharging curve of grapheme foam nickel electrode prepared by embodiment 1.
Embodiment
The present invention provides a kind of preparation method of grapheme foam nickel electrode, mainly using cyclic voltammetric and constant potential also
The technology that original is combined, in graphene oxide dispersion and glycine-HCI buffer solution, using nickel foam as substrate, obtains
Grapheme foam nickel electrode, is that a kind of electrochemical reduction using simplicity obtains the good porous graphene nickel foam of capacitive property
The preparation method of electrode.Graphene electrodes are which solved in ultracapacitor energy storage device application process, complex production process,
The problem of energy consumption is big.Realize the batch production of the Graphene electrodes of nickel foam Auxiliary support, simple flow, improves specific capacitance.
Specific method be nickel foam is cleaned, it is dry after as working electrode, using saturated calomel electrode as reference electrode, platinum
Piece is to electrode, in graphene oxide dispersion, is scanned using cyclic voltammetry and graphene oxide foam nickel electrode is made, done
After dry, in glycine hydrochloride buffer solution, constant potential drastic reduction is carried out, obtains grapheme foam nickel electrode.Wherein use
Cyclic voltammetry is tentatively reduced, and carrying out second using glycine-HCI buffer solution afterwards reduces, in this reduction process
In be conducive to graphene oxide molecule and obtain electronics and H under the action of constant potential electric field+Ion, functional group are by carboxyl reduction
Carbonyl, and it is reduced further into hydroxyl.And as needed can be by varying cyclic voltammetry scan time, speed, and change permanent
Potential voltage, to adjust the performance of grapheme foam nickel electrode.The glycine-HCI buffer solution that the present invention uses is through excessive
Amount experiment determines, by the experiment of a variety of buffer solutions, finds only have glycine-HCI buffer solution to effectively improve graphene
The capacitive property of foam nickel electrode, the pH value of buffer solution are also to determine that effect is preferable at 3~5 by many experiments.Utilize
The effect of constant pressure electric field, can produce the effect of uniform electric field force, the product stable and uniform of acquisition, and preparation method it is easy to operate,
It is convenient.
Nickel foam is cleaned in the method for the present invention, it is therefore an objective to allow nickel foam to be totally easy to react, it is preferable that to use successively
Deionized water, dilute hydrochloric acid, absolute ethyl alcohol, acetone are optimal, 3~50min of scavenging period, it is highly preferred that using being cleaned by ultrasonic, are surpassed
The optional 50-100kHz of frequency range of sound.
It is dry, it is mainly used for removing residual liquid in nickel foam, easy to subsequent reactions.Under room temperature naturally dry also can,
In order to accelerate drying, uploaded suitable for batch, optional 60~110 DEG C of dry temperature, dry 10~60min.In order to further
Accelerate reaction, can use and be dried under vacuum.Likewise, obtained graphene oxide foam nickel electrode is dried
When, preferably 80~115 DEG C of dry temperature, more preferably using vacuum condition, drying time is 10~60min.
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by embodiment, to this hair
It is bright to be described in detail.
The preparation of 1 grapheme foam nickel electrode of embodiment
The preparation method of grapheme foam nickel electrode, concrete operations are as follows：
(1) deionized water is utilized, dilute hydrochloric acid, absolute ethyl alcohol, acetone is respectively washed each 5min of nickel foam, afterwards 80 DEG C of vacuum
Middle dry 30min.
(2) graphene oxide dispersion is prepared：The graphene oxide that material rate according to 2g graphite is made into 4g/L is water-soluble
Liquid.Specifically, 2g graphite powders are weighed, using improved Hummer methods (reference can be made to Xu Juan., Wei Xicheng, Cao
Jianyu, et al., Electrochimica Acta, 2015,152:Graphene oxide 391-397.) is prepared, then ultrasound stripping
Graphene oxide dispersion is made from 30min and is diluted to 500mL.
(3) cyclic voltammetry is utilized, using nickel foam as working electrode, using saturated calomel electrode as reference electrode, platinized platinum is
To electrode, in graphene dispersing solution, in -1.4~0.6V, 50mV/s's sweeps under speed, the circle of scanning 50.
Under (4) 110 DEG C of vacuum conditions after dry 30min, graphene oxide foam nickel electrode is obtained.
(5) graphene oxide foam nickel electrode is placed in glycine/hydrochloric acid buffer solution of pH 3.6, -1.1V conditions
Lower progress constant potential drastic reduction 75min；Afterwards grapheme foam nickel electrode is obtained after 110 DEG C of dry 30min dryings.
Wherein the collocation method of glycine/hydrochloric acid buffer solution of pH 3.6 is 50ml 0.2mol L-1Glycine adds 5ml
Concentration is 0.2mol L-1Hydrochloric acid, is diluted with water 200ml.
The grapheme foam nickel electrode that will be prepared, using the 510PFT type infrared spectrometers of Nicolet companies of the U.S.,
Utilize KBr pressed disc methods.Test wave-number range is 400~4000cm-1, the infrared spectrogram measured is as shown in Figure 1,1718cm-1Place
C=O absworption peaks and 852cm in carboxyl and carbonyl-1The absworption peak of place O-C=O almost disappears, and illustrates that reduction effect is bright
Aobvious, quality is good, without impurity.
It is selected using the LabRAMXploRA type Raman spectrometers of French HORIBA JOBIN YVON S.A.S companies
Excitation wavelength 532nm, scanning range are 500~3200cm-1.The Raman spectrogram of acquisition is as shown in Fig. 2, wherein 1345cm-1Place
D peaks be due to sp caused by defect3The carbon atom of hydridization produces.Its presence illustrate graphene have certain randomness and
A certain amount of oxygen-containing functional group.This randomness is related with the three-dimensional character of nickel foam.Illustrate dispersiveness between graphene film
It is good.Avoid agglomeration.Be conducive to ion transmission, thus add capacitive property.1580cm-1The G peaks at place mainly due to
sp2Telescopic vibration produces in the C=C atomic planes of hydridization.
Using the VG ESCABmk-2 type x-ray photoelectron spectroscopies (X-ray of Japanese VGScientific Ltd. companies
Photoelectron spectroscopy, XPS) XPS tests are carried out to sample powder.Its XPS spectrum figure as shown in figure 3, its
It is O at middle 530eV1sPeak, is C at 280eV1sPeak.Illustrate that there are a small amount of oxygen element in graphene.And a small amount of oxygen-containing functional group
The avtive spot beneficial to increase ion exchange is there are, improves the capacitive property of Graphene electrodes.As shown in Figure 6, specific capacitance
Reach 493F g-1。
Using Dutch Philips-FEI companies Sirion200 type field emission scanning electron microscopes to sample surface morphology
Observed.Obtained scanning electron microscope (SEM) photograph is as shown in fig. 4, it can be seen that the graphene film such as cicada's wings is adhered to nickel foam table
Face.
Using grapheme foam nickel electrode manufactured in the present embodiment as positive and negative anodes, with the Na of 1mol/L2SO4Solution is electrolyte
It is assembled into symmetric form ultracapacitor.Its energy density, for power density as shown in figure 5, in figure, ordinate is energy work rate
(Energy Density), abscissa are power density (Power Density), wherein, the current density of nine points is respectively
1.4,2.9,4.3,5.8,7.2,10.1,11.6,13.0,14.5Ag-1.By understanding that its energy density can be to 74Wh Kg in figure-1。
Using grapheme foam nickel electrode manufactured in the present embodiment as working electrode, saturated calomel electrode is reference electrode, platinum
Piece is to electrode, using CHI660D electrochemical workstations, in the Na that concentration is 1mol/L2SO4In solution, constant current charge and discharge is carried out
Electrical testing.Test current density is 2.3Ag-1.Test result, i.e. charging and discharging curve are as shown in Figure 6.According to following formula meter
Calculate, specific capacitance 493Fg-1。
Wherein, i is discharge current, and t refers to discharge time, and m is active material quality, and △ V refer to electrochemical window.
The theoretical capacitance of graphene is 350F g in the capacitor-1Left and right, the present invention reach 493.5Fg-1, significantly
Improve the capacitive property of grapheme foam nickel electrode.
Embodiment 2
1) it is 1cm to select area2Nickel foam is substrate, successively with deionized water, dilute hydrochloric acid, absolute ethyl alcohol, acetone difference
Supersound washing 15min, 5min, 15min, 5min, then in 110 DEG C of dry 10min.The frequency of supersound washing can use 50~
100kHz。
2) graphene oxide dispersion：Take the graphene oxide solution of 2g/L.
It should be noted that the graphene oxide dispersion in the present invention is the oxidation step used in oxidation-reduction method
Obtain, that is, refer to native graphite and the reaction of strong acid and oxidizing species generating graphite oxide (GO), by ultrasonic disperse system
For into graphene oxide (mono-layer graphite oxide) solution, the concentration of needs is diluted to, the concentration of graphene oxide is with initial institute
Subject to the quality of graphite, be distributed to 2-4g/L, in oxidizing process can the graphite of the loss of energy do not count.
3) cyclic voltammetry is utilized, using nickel foam as working electrode, using saturated calomel electrode as reference electrode, platinized platinum is pair
Electrode, in graphene oxide dispersion, in -1.2V, 30mV/s's sweeps under speed, the circle of scanning 100.
4) 100 DEG C of dry 20min, obtain graphene oxide foam nickel electrode.
5) graphene oxide foam nickel electrode is placed in glycine/hydrochloric acid buffer solution of pH 3.4, wherein glycine
Concentration be 0.05mol L-1, constant potential drastic reduction 45min is carried out under the conditions of -0.8V；Stone is obtained after 100 DEG C of dry 10min
Black alkene foam nickel electrode.
The grapheme foam nickel electrode prepared is in the Na that concentration is 0.75mol/L2SO4In solution, carry out constant current and fill
Discharge test, test current density are 2.3Ag-1；It is 477.1F g to measure specific capacitance-1。
The above described is only a preferred embodiment of the present invention, being not the limitation that other forms are done to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of preparation method of grapheme foam nickel electrode, it is characterised in that this method is to clean nickel foam, make after drying
For working electrode, in graphene oxide dispersion, scanned using cyclic voltammetry and graphene oxide foam nickel electrode is made, done
After dry, in glycine-HCI buffer solution, constant potential reduction is carried out, obtains grapheme foam nickel electrode.
2. preparation method as claimed in claim 1, it is characterised in that it is described cleaning for successively using deionized water, dilute hydrochloric acid,
Absolute ethyl alcohol, acetone are respectively washed.
3. preparation method as claimed in claim 2, it is characterised in that the cleaning, which uses, to be cleaned by ultrasonic, scavenging period each 3~
50min, the mass fraction of the dilute hydrochloric acid is 1~5%.
4. such as the preparation method any one of claim 1-3, it is characterised in that after the cleaning it is dry use temperature for
It is 60~110 DEG C, dry 10~60min, dry under vacuum or non-vacuum condition.
5. such as the preparation method any one of claim 1-4, it is characterised in that oxygen in the graphene oxide dispersion
The mass concentration of graphite alkene is 2~4g/L.
6. such as the preparation method any one of claim 1-5, it is characterised in that the condition of the cyclic voltammetry be with
Saturated calomel electrode is reference electrode, and for platinized platinum to be -1.4~0.6V to electrode, voltage, it is to be scanned under 5~80mV/s to sweep speed.
7. such as the preparation method any one of claim 1-6, it is characterised in that the graphene oxide foam nickel electrode
Drying use 80~115 DEG C of temperature, vacuum or non-vacuum condition drying, drying time is 10~60min.
8. such as the preparation method any one of claim 1-7, it is characterised in that the glycine hydrochloride buffer solution
The scope of pH value is 3~5, the final concentration of 0.03molL of the glycine-1~0.2mol L-1。
9. such as the preparation method any one of claim 1-8, it is characterised in that the voltage of constant potential reduction for-
1.6~-0.8V, 15~120min of recovery time.
10. grapheme foam nickel electrode prepared by the method as any one of claim 1-9 is in ultracapacitor, lithium ion
Application in battery, fuel cell and biology sensor.
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