CN107967998B - Preparation method of graphene foam nickel electrode - Google Patents
Preparation method of graphene foam nickel electrode Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 168
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 118
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 84
- 239000006260 foam Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 17
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- 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 13
- 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
- 239000004471 Glycine Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 1
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- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a preparation method and application of a graphene foam nickel electrode. The preparation method comprises the steps of cleaning and drying the foamed nickel to be used as a working electrode, scanning the working electrode in a graphene oxide dispersion liquid by using a cyclic voltammetry method to prepare a graphene oxide foamed nickel electrode, drying the graphene oxide foamed nickel electrode, and carrying out constant-potential reduction in a glycine-hydrochloric acid buffer solution to obtain the graphene foamed nickel electrode. Compared with other preparation methods of graphene electrodes, the preparation method of the graphene foam nickel electrode has the advantages of cheap raw materials, no pollution, environmental friendliness and convenience for mass production. The graphene foam nickel electrode supported by the foam nickel shows good capacitance performance in neutral electrolyte, and can be used in the field of energy storage.
Description
Technical Field
The invention belongs to the technical field of supercapacitors, and particularly relates to a preparation method and application of a graphene foam nickel electrode.
Background
The graphene is through carbon atom sp2The hybridization forms a honeycomb-shaped network structure which has the thickness of a single atomic layer and is a very thin two-dimensional structural material. The theoretical specific surface area value is very high. Due to the special properties of graphene in the aspects of light, heat, electricity and the like, such as higher specific surface area and excellent conductivity, the graphene has wide application space in the aspects of supercapacitors, batteries and the like.
There are many methods for preparing graphene, including a mechanical exfoliation method, a Chemical Vapor Deposition (CVD) method, an oxidation-reduction method, a solvent exfoliation method, a solvothermal method, and the like. The mechanical stripping method is to directly cut the graphene sheet from a larger crystal; chemical Vapor Deposition (CVD) refers to a process in which a reactant reacts chemically in a gaseous state to produce a solid material that is deposited on the surface of a heated solid substrate to produce a solid material. A tubular simple deposition furnace using nickel as a substrate is provided, carbon-containing gas is introduced, such as: the carbon-hydrogen compound is decomposed into carbon atoms at high temperature and deposited on the surface of the nickel to form graphene, and the graphene film is separated from the nickel sheet through slight chemical etching to obtain the graphene film; the oxidation-reduction method is that natural graphite reacts with strong acid and strong oxidizing substances to generate Graphite Oxide (GO), graphene oxide (single-layer graphite oxide) is prepared through ultrasonic dispersion, and reducing agents are added to remove oxygen-containing groups on the surface of the graphite oxide, such as carboxyl, epoxy and hydroxyl, so as to obtain graphene; the oxidation-reduction method has the defects that the macro preparation is easy to cause waste liquid pollution, and the prepared graphene has certain defects, so that the loss of partial electrical properties of the graphene is caused, and the application of the graphene is limited; the principle of the solvent stripping method is that a small amount of graphite is dispersed in a solvent to form a low-concentration dispersion liquid, van der waals force between graphite layers is destroyed by the action of ultrasonic waves, and the solvent can be inserted between the graphite layers to carry out layer-by-layer stripping, so that the graphene is prepared. The method does not damage the structure of the graphene like an oxidation-reduction method, can prepare high-quality graphene, and has the defect of low yield; the solvothermal method is an effective method for preparing materials by heating a reaction system to a critical temperature (or close to the critical temperature) and generating high pressure in the reaction system in a specially-made closed reactor (high-pressure kettle) by using an organic solvent as a reaction medium, and solves the problem of large-scale preparation of graphene and brings about negative influence of low conductivity. The materials of graphene are different, and how to prepare graphene electrodes with high mass production quality by using graphene is still a difficult problem.
The existing graphene electrode is prepared into a film by using high vacuum, high pressure, plasma and other technologies, and some films need to be separated from a substrate, so that the steps are complex, the process is complex, the energy consumption is high, and the graphene electrode is not suitable for batch production; in addition, the brushing method is adopted to brush the brushing liquid on the foamed nickel, the brushing liquid is easy to cover unevenly in the brushing process, and then the drying is needed, the repeated operation is needed, the operation is complex, and the quality of the finally obtained product is not very stable.
Disclosure of Invention
Technical problem to be solved
In order to solve the above problems in the prior art, the present invention provides a method for preparing a graphene nickel foam electrode.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a preparation method of a graphene foamed nickel electrode comprises the steps of cleaning and drying foamed nickel to serve as a working electrode, scanning the working electrode in a graphene oxide dispersion liquid by using a cyclic voltammetry method to obtain the graphene oxide foamed nickel electrode, drying the graphene oxide foamed nickel electrode, and carrying out constant potential reduction in a glycine-hydrochloric acid buffer solution to obtain the graphene foamed nickel electrode.
In the preparation method of the graphene nickel foam electrode, preferably, the cleaning is respectively performed by sequentially using deionized water, dilute hydrochloric acid, absolute ethyl alcohol and acetone. Furthermore, the foamed nickel can be subjected to ultrasonic cleaning by using the solution, and the cleaning time is 3-50 min respectively. The frequency range of the ultrasonic wave is 50-100 kHz.
In the preparation method of the graphene nickel foam electrode, the diluted hydrochloric acid preferably accounts for 1-5% by mass.
According to the preparation method of the graphene nickel foam electrode, preferably, the drying after cleaning is performed at the temperature of 60-110 ℃ for 10-60 min, and more preferably, the drying is performed in vacuum.
In the preparation method of the graphene nickel foam electrode, the mass concentration of the graphene oxide in the graphene oxide dispersion liquid is preferably 2-4 g/L.
According to the preparation method of the graphene nickel foam electrode, preferably, the cyclic voltammetry is performed under the conditions that a saturated calomel electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, the voltage is-1.4-0.6V, and the sweep rate is 5-80 mV/s. Preferably, 30-150 scanning circles are good.
According to the preparation method of the graphene foam nickel electrode, preferably, the graphene oxide foam nickel electrode is dried at the temperature of 80-115 ℃ under a vacuum condition for 10-60 min.
In the preparation method of the graphene nickel foam electrode, preferably, the pH value of the glycine hydrochloric acid buffer solution is 3-5, and the concentration of glycine is 0.03mol L-1～0.2mol L-1。
According to the preparation method of the graphene nickel foam electrode, preferably, the voltage of constant-potential reduction is-1.6 to-0.8V, and the reduction time is 15 to 120 min.
The graphene nickel foam electrode prepared by the method is applied to supercapacitors, lithium ion batteries, fuel cells and biosensors.
(III) advantageous effects
The invention has the beneficial effects that:
compared with other graphene electrode preparation methods, the preparation method of the graphene foam nickel electrode adopts a mode of combining cyclic voltammetry scanning and constant potential reduction in a grading manner, and obtains the graphene foam electrode with high capacitive performance by fewer raw materials and process steps and a simpler and more convenient operation mode. The preparation method has the advantages of cheap raw materials, little pollution, simple and convenient operation, environmental protection and convenient mass production. And the performance of the graphene electrode can be adjusted by changing the cyclic voltammetry scanning time, rate and constant potential voltage. The prepared graphene foam nickel electrode is good in quality, has a small amount of oxygen-containing functional groups, is beneficial to increasing active sites of ion exchange, and improves the capacitance performance of the graphene electrode.
The method solves the problems of complex production process, high energy consumption, unstable product and the like of the graphene electrode in the application process of energy storage devices such as a super capacitor and the like. The invention realizes the batch production of the graphene electrode supported by the foam nickel, simplifies the process and improves the specific capacitance. The prepared graphene foamed nickel electrode supported by foamed nickel shows good capacitance performance in neutral electrolyte, and can be used in the field of energy storage. Specifically, the prepared graphene foam nickel electrode can be used in the fields of super capacitors, lithium ion batteries, fuel cells, biosensors and the like. The graphene foam nickel electrode can also react with lithium ions, is beneficial to inducing the insertion of the lithium ions, is applied to the cathode of a lithium primary battery, and avoids the water absorbability when graphite oxide is used as an electrode material and the toxicity when graphite fluoride is used as the electrode material.
Drawings
Fig. 1 is an infrared spectrum of the graphene nickel foam electrode prepared in example 1;
fig. 2 is a raman spectrum of the graphene nickel foam electrode prepared in example 1;
fig. 3 is an XPS spectrum of the graphene nickel foam electrode prepared in example 1;
FIG. 4 is a scanning electron micrograph of the graphene nickel foam electrode prepared in example 1;
fig. 5 shows the energy density and power density of a supercapacitor made of the graphene nickel foam electrode prepared in example 1;
fig. 6 is a charge and discharge curve of the graphene nickel foam electrode prepared in example 1.
Detailed Description
The invention provides a preparation method of a graphene foamed nickel electrode, which mainly adopts a technology of combining cyclic voltammetry and constant potential reduction, obtains the graphene foamed nickel electrode by taking foamed nickel as a substrate in a graphene oxide dispersion solution and a glycine-hydrochloric acid buffer solution, and is a preparation method for obtaining a porous graphene foamed nickel electrode with good capacitance performance by utilizing simple and convenient electrochemical reduction. The problems that the production process is complex and the energy consumption is high in the application process of the graphene electrode in the super capacitor energy storage device are solved. The mass production of the graphene electrode supported by the foam nickel is realized, the flow is simplified, and the specific capacitance is improved.
The method comprises the steps of cleaning and drying foamed nickel to be used as a working electrode, taking a saturated calomel electrode as a reference electrode and a platinum sheet as a counter electrode, scanning the graphene oxide foamed nickel electrode in a graphene oxide dispersion liquid by using a cyclic voltammetry method, drying the graphene oxide foamed nickel electrode, and carrying out constant-potential deep reduction in a glycine hydrochloric acid buffer solution to obtain the graphene foamed nickel electrode. Wherein the initial reduction is carried out by cyclic voltammetry, and then glycine-hydrochloric acid buffer solution is adoptedThe liquid is subjected to secondary reduction, and the graphene oxide molecules are favorably subjected to electron and H under the action of a constant potential electric field in the reduction process+Ions, functional groups are reduced from carboxyl to carbonyl and further to hydroxyl. And the performance of the graphene foam nickel electrode can be adjusted by changing the cyclic voltammetry scanning time and rate and changing the constant potential voltage according to the needs. The glycine-hydrochloric acid buffer solution adopted by the invention is determined through a large number of experiments, and through the experiments of various buffer solutions, the fact that only the glycine-hydrochloric acid buffer solution can effectively improve the capacitance performance of the graphene foam nickel electrode is found, and the pH value of the buffer solution is determined through a large number of experiments to be better at 3-5. The action of the constant voltage electric field can generate uniform electric field action, the obtained product is stable and uniform, and the preparation method is simple and convenient to operate.
According to the method, the foam nickel is cleaned, the purpose is to enable the foam nickel to be clean and easy to react, preferably, deionized water, dilute hydrochloric acid, absolute ethyl alcohol and acetone are sequentially adopted as the best materials, the cleaning time is 3-50 min, more preferably, ultrasonic cleaning is adopted, and the frequency range of ultrasonic cleaning can be selected from 50-100 kHz.
And drying, which is mainly used for removing residual liquid on the foamed nickel and is convenient for subsequent reaction. The drying process can be carried out naturally at normal temperature, and is suitable for batch uploading in order to accelerate drying, wherein the drying temperature can be 60-110 ℃, and the drying time is 10-60 min. To further accelerate the reaction, drying under vacuum may be employed. Similarly, when the prepared graphene oxide foam nickel electrode is dried, the drying temperature is preferably 80-115 ℃, more preferably, the vacuum condition is adopted, and the drying time is 10-60 min.
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Example 1 preparation of graphene nickel foam electrode
The preparation method of the graphene foam nickel electrode specifically comprises the following operations:
(1) the foam nickel is respectively cleaned by deionized water, dilute hydrochloric acid, absolute ethyl alcohol and acetone for 5min, and then dried in vacuum at 80 ℃ for 30 min.
(2) Preparing a graphene oxide dispersion liquid: preparing 4g/L graphene oxide aqueous solution according to the raw material proportion of 2g of graphite. Specifically, 2g of graphite powder is weighed, graphene oxide is prepared by an improved Hummer method (see Xu Juan, Wei Xicheng, CaoJianyu, et al, Electrochimica Acta, 2015, 152: 391-.
(3) And scanning for 50 circles in graphene dispersion liquid at a scanning speed of-1.4-0.6V and 50mV/s by using a cyclic voltammetry method and using foamed nickel as a working electrode, a saturated calomel electrode as a reference electrode and a platinum sheet as a counter electrode.
(4) And drying the graphite electrode for 30min at the temperature of 110 ℃ under a vacuum condition to obtain the graphene oxide foam nickel electrode.
(5) Placing the graphene oxide foam nickel electrode in glycine/hydrochloric acid buffer solution with the pH value of 3.6, and carrying out constant potential deep reduction for 75min under the condition of-1.1V; and drying at 110 ℃ for 30min to obtain the graphene foamed nickel electrode.
Wherein the preparation method of glycine/hydrochloric acid buffer solution with pH of 3.6 is 50ml and 0.2mol L-1Glycine plus 5ml concentration of 0.2mol L-1Hydrochloric acid, and water was added to dilute to 200 ml.
The prepared graphene nickel foam electrode is prepared by adopting a 510PFT type infrared spectrometer of Nicolet company in America and utilizing a KBr tabletting method. The test wave number range is 400-4000 cm-1The measured infrared spectrum is shown in FIG. 1, 1718cm-1Absorption peaks at carboxyl group and C ═ O in carbonyl group and 852cm-1The absorption peak of O-C-O almost completely disappears, which shows that the reduction effect is obvious, the quality is good and no impurity exists.
The method uses LabRAMXploRA type Raman spectrometer of HORIBA JOBIN YVON S.A.S. of France, and the selected excitation wavelength is 532nm, and the scanning range is 500-3200 cm-1. The obtained Raman spectrum is shown in FIG. 2, in which 1345cm-1D peak at (b) is sp due to defect3The hybridized carbon atom is generated. Its presence indicates that graphene has a certain disorder and a certain amount of oxygen-containing functional groups. The three-dimensional characteristics of the disorder and the foam nickelIt is related to sex. The good dispersibility among the graphene films is demonstrated. Avoiding the agglomeration phenomenon. Ion transport is facilitated, thereby increasing the capacitive performance. 1580cm-1The G peak at (A) is mainly due to sp2Hybrid C ═ C atomic plane telescopic vibration is generated.
The sample powder was subjected to XPS test using VG ESCAMK-2 model X-ray photoelectron spectrometer (XPS) of VGscientific Ltd. in Japan. The XPS spectrum is shown in FIG. 3, in which 530eV is O1sPeak, C at 280eV1sPeak(s). Indicating that a small amount of oxygen is present in the graphene. And the existence of a small amount of oxygen-containing functional groups is beneficial to increasing the active sites of ion exchange and improving the capacitance performance of the graphene electrode. As shown in fig. 6, the specific capacitance reaches 493F g-1。
The surface topography of the sample was observed using a field emission scanning electron microscope model Sirion200 from Philips-FEI, the netherlands. The scanning electron micrograph obtained is shown in fig. 4, and it can be seen that a graphene film like cicada wing adheres to the surface of the nickel foam.
The graphene nickel foam electrode prepared in the embodiment is used as a positive electrode and a negative electrode, and 1mol/L of Na is used2SO4The solution is an electrolyte to assemble a symmetrical super capacitor. The Energy Density and Power Density are shown in fig. 5, in which the ordinate is Energy Power (Energy Density) and the abscissa is Power Density (Power Density), and the current densities at nine points are 1.4, 2.9, 4.3, 5.8, 7.2, 10.1, 11.6, 13.0, and 14.5A · g-1. The energy density can reach 74Wh Kg-1。
The graphene nickel foam electrode prepared in the embodiment is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and a CHI660D electrochemical workstation is used for processing Na with the concentration of 1mol/L2SO4In the solution, constant current charge and discharge test was performed. The test current density is 2.3 A.g-1. The test results, i.e., the charge and discharge curves, are shown in fig. 6. The specific capacitance was 493Fg, calculated according to the following formula-1。
Where i is a discharge current, t is a discharge time, m is an active material mass, and △ V is a potential window.
The theoretical capacitance value of graphene in the capacitor is 350F g-1On the other hand, the present invention reaches 493.5F g-1And the capacitance performance of the graphene foam nickel electrode is greatly improved.
Example 2
1) Selecting the area of 1cm2The foamed nickel is taken as a substrate, ultrasonic washing is carried out for 15min, 5min, 15min and 5min respectively by deionized water, diluted hydrochloric acid, absolute ethyl alcohol and acetone, and then drying is carried out for 10min at 110 ℃. The frequency of ultrasonic washing can be 50-100 kHz.
2) Graphene oxide dispersion liquid: taking 2g/L of graphene oxide solution.
It should be noted that the graphene oxide dispersion liquid in the present invention is obtained by an oxidation step in an oxidation-reduction method, that is, natural graphite reacts with strong acid and strong oxidizing substances to generate Graphite Oxide (GO), and the graphite oxide (single-layer graphite oxide) solution is prepared by ultrasonic dispersion and diluted to a desired concentration, wherein the concentration of the graphene oxide is based on the mass of the graphite used initially and is dispersed to 2-4g/L, and the graphite possibly lost in the oxidation process is not counted.
3) By utilizing cyclic voltammetry, foamed nickel is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and 100 circles of scanning is carried out in graphene oxide dispersion liquid at a scanning speed of-1.2V and 30 mV/s.
4) And drying at 100 ℃ for 20min to obtain the graphene oxide foam nickel electrode.
5) Placing the graphene oxide foam nickel electrode in glycine/hydrochloric acid buffer solution with the pH value of 3.4, wherein the concentration of glycine is 0.05mol L-1Carrying out constant potential deep reduction for 45min under the condition of-0.8V; and drying at 100 ℃ for 10min to obtain the graphene foamed nickel electrode.
Na with concentration of 0.75mol/L is used for preparing the obtained graphene nickel foam electrode2SO4In solution, go on constantlyThe current density of the current charge and discharge test is 2.3 A.g-1(ii) a Measured specific capacitance of 477.1F g-1。
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (6)
1. A preparation method of a graphene foamed nickel electrode is characterized in that foamed nickel is cleaned and dried to serve as a working electrode, the graphene oxide foamed nickel electrode is prepared by scanning in a graphene oxide dispersion liquid through a cyclic voltammetry method, and after drying, constant potential reduction is carried out in a glycine-hydrochloric acid buffer solution to obtain the graphene foamed nickel electrode;
the cleaning is respectively cleaning by sequentially adopting deionized water, dilute hydrochloric acid, absolute ethyl alcohol and acetone;
the cyclic voltammetry is carried out under the conditions that a saturated calomel electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, the voltage is-1.4-0.6V, and the scanning speed is 5-80 mV/s;
the mass concentration of graphene oxide in the graphene oxide dispersion liquid is 2-4 g/L;
the pH value of the glycine hydrochloric acid buffer solution is within the range of 3-5, and the final concentration of glycine is 0.03mol L-1～0.2mol L-1。
2. The preparation method of claim 1, wherein the cleaning is ultrasonic cleaning, the cleaning time is 3-50 min each, and the mass fraction of the dilute hydrochloric acid is 1-5%.
3. The method according to claim 1, wherein the drying after the cleaning is performed at a temperature of 60 to 110 ℃, for 10 to 60min, and under a vacuum or non-vacuum condition.
4. The preparation method of claim 1, wherein the graphene oxide foam nickel electrode is dried at 80-115 ℃ under vacuum or non-vacuum conditions for 10-60 min.
5. The preparation method of claim 1, wherein the voltage of the constant potential reduction is-1.6 to-0.8V, and the reduction time is 15 to 120 min.
6. Use of the graphene nickel foam electrode prepared according to any one of claims 1 to 5 in supercapacitors, lithium ion batteries, fuel cells and biosensors.
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