CN114360923A - Preparation method of nickel oxide composite electrode material - Google Patents
Preparation method of nickel oxide composite electrode material Download PDFInfo
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Abstract
In order to solve the problem of low capacity of nickel oxide in the prior art, the invention provides a preparation method of a nickel oxide composite electrode material, which comprises the following steps: preparing graphite oxide, preparing graphene by reducing the graphite oxide, preparing a nickel oxide composite material, and post-treating the nickel oxide composite material. The invention firstly proposes that the high-reduction-degree high-defect-degree graphene is used for modifying nickel oxide, and the nickel oxide composite material is rapidly subjected to heat treatment under the microwave condition by utilizing the strong microwave absorption and conversion capability of the high-reduction-degree high-defect graphene, so that the conductivity of the nickel oxide is greatly improved, the low-consumption high-efficiency heat treatment of the nickel oxide composite material is realized, and the nickel oxide composite electrode material with high electrochemical activity is prepared.
Description
Technical Field
The invention relates to the field of electrode materials, in particular to a preparation method of a nickel oxide composite electrode material.
Background
With the rapid increase of the world demand for new energy technologies, the demand for new energy devices such as super capacitors, lithium batteries, etc. with high capacity, high power, high energy density and long service life is becoming greater and greater. The key to realizing new energy devices is the energy storage capacity of electrode materials. Therefore, designing and obtaining high-capacity electrode materials become the focus of current new energy device development.
Among them, nickel oxide is widely developed for use in supercapacitors and batteries because of its high theoretical energy storage capacity. However, although nickel oxide possesses a high theoretical capacity, it is difficult to obtain a high capacity in a practical process, thus limiting its further practical use.
In order to obtain nickel oxide, several effective methods for preparing nickel oxide have been developed over several decades, such as hydrothermal method, solvothermal method, high-temperature pyrolysis method, and the like. By the methods, nickel oxide materials with different shapes, different scales and different dimensions are successfully obtained. Meanwhile, various post-treatment technologies are developed for optimizing and improving the performance of the nickel oxide material. Thus, nickel oxide based materials with different energy storage properties were obtained.
Patent CN103943379A is a preparation method of a graphene-loaded flower-like porous nickel oxide composite material, which is typically characterized in that nickel oxide sheets are assembled into a flower-like structure and are compounded with graphene sheet layers, graphene has good conductivity as a matrix skeleton, and flower-like nickel oxide microspheres can be loaded on graphene sheets to realize good conductivity, thereby improving apparent conductivity of the composite material. The composite material has a capacitance of 413F/g at a current density of 200mA/g at most.
The invention discloses a preparation method of a patent CN103632857A nickel oxide/reduced graphene oxide nanosheet composite material, which takes multi-wall carbon nanotubes (WMCNTs) as raw materials, and adopts a Hummer method to oxidize and obtain easily-dispersed graphite oxide nanosheets (CNGO) with a lamellar structure; ultrasonically dispersing graphite oxide nanosheets (CNGO) and Ni (NO3) 2.6H 2O in an ethanol solvent, and carrying out solvothermal reaction for 10-12H at the temperature of 140-180 ℃; cooling to room temperature, filtering, washing with water and absolute ethyl alcohol, and vacuum drying to obtain a precursor composite material; and then, carrying out heat treatment on the precursor composite material for 3-5 h at 200-250 ℃ in an air atmosphere to obtain the nickel oxide/reduced graphene oxide nanocomposite. The specific current is 1A/g, and the charging and discharging test is carried out on the specific current, and the test result is as follows: the specific capacitance value is 714-1010F/g.
Therefore, the specific capacity of the nickel oxide composite electrode prepared by the prior art is far lower than the theoretical value (<1500F/g), and the operation of some methods is complex and the equipment requirement is high. Therefore, how to obtain the nickel oxide material with high specific capacity is still a key technical problem to be solved urgently.
Disclosure of Invention
In order to solve the problem of low capacity of the nickel oxide composite electrode in the prior art, the invention provides a preparation method of a nickel oxide composite electrode material, so that the nickel oxide composite electrode with high capacity is obtained.
The invention aims to realize the technical scheme that the preparation method of the nickel oxide composite electrode material comprises the following steps:
s1, preparation of graphite oxide: preparing graphite oxide for later use by using crystalline flake graphite as a precursor through a chemical stripping method;
s2, preparing graphene by reducing graphite oxide: taking graphite oxide, and carrying out reduction treatment on the graphite oxide to prepare graphene for later use;
s3, preparation of a nickel oxide composite material: taking graphene, urea and nickel chloride (NiCl)2·6H2O) is dispersed in water, and the nickel oxide/graphene composite material is prepared for standby through hydrothermal reaction;
s4, post-treatment of the nickel oxide composite material: and (3) performing microwave treatment on the nickel oxide/graphene composite material to prepare the nickel oxide composite electrode material.
Wherein, the chemical stripping method in the step S1 comprises Hummers method, Standemamier method and Brodie method, and the graphite oxide or the graphene oxide is prepared by oxidizing the scale graphite.
Wherein the graphite oxide prepared in the step S1 has an oxygen atom content of 25 to 30 at.%.
The reduction treatment in the step S2 includes a flame method, a flame method and a microwave method, and the graphite oxide or the graphene oxide is reduced to obtain the high-reduction-degree and high-defect-degree graphene.
Wherein in the flame method and the microwave method in the step S2, the microwave treatment time is 3-9S.
Wherein the graphene prepared in the step S2 has an oxygen atom content of 3.1 to 12 at.%.
Wherein, in the step S3, the graphene, the urea and the NiCl are adopted2·6H2The mass ratio of O is 1: 4: 4.
wherein the hydrothermal reaction time in the step S3 is 4-12 h; the temperature of the hydrothermal reaction is 140-180 ℃.
Wherein the microwave treatment time in the step S4 is 3-15S; the power of the microwave treatment is 600-1200W.
The invention firstly proposes that the high-reduction high-defect graphene is used for modifying nickel oxide, and the uniform and rapid heat treatment of the nickel oxide composite material under the microwave condition is realized by utilizing the strong microwave absorption and conversion capability of the high-reduction high-defect graphene. A large number of defects formed in the graphene obviously change the electronic structure of the graphene, so that the effect between the graphene and the nickel oxide can be enhanced, the capability of the graphene for absorbing and converting microwaves into heat can be changed, and the graphene can be used as an active site of an electrochemical reaction. The high reduction of graphite alkene is favorable to making graphite alkene obtain strong microwave absorption and convert the ability into heat on the one hand, is favorable to making graphite alkene obtain strong heat conductivity on the one hand to make its heat energy that absorbs microwave conversion can in time be passed to nickel oxide, realize the rapid thermal treatment of nickel oxide, the high reduction of graphite alkene makes it have high conductivity simultaneously, thereby can effectively promote the electric conductivity of nickel oxide. In addition, the high reduction of graphene can also prevent the interaction between nickel oxide and graphene from being weakened by gas released by the decomposition of oxygen-containing functional groups on the surface of graphene during microwave treatment. Therefore, the electric conductivity of the nickel oxide is greatly improved through the strategy, and low-consumption and high-efficiency heat treatment of the nickel oxide composite material is realized, so that the nickel oxide composite electrode material with high activity is prepared. The method is simple to operate, low in consumption and high in efficiency, and can be suitable for large-scale treatment and optimization of nickel oxide materials and can also be used for conductivity improvement and heat treatment of other materials. The preparation process of the graphite oxide, the reduction process of the graphite oxide, the hydrothermal reaction process and the microwave treatment process are simple and easy to operate, and the used raw materials, reagents and equipment are all obtained from commercial sources, so that the source is wide and the cost is low.
The invention greatly improves the capacity of the nickel oxide electrode material, solves the problems of the nickel oxide electrode material constructed by the prior method, and the prepared product has good conductivity and high activity, has high specific capacitance for a super capacitor, can obtain the specific capacitance close to a theoretical value at most, and has the following advantages: the specific capacitance is ultrahigh, and is 1500-2500F/g; ② the conductivity is good, the charge transfer impedance is 0.5-1.5 omega.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of high-reduction high-defect graphene prepared in example 1;
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) graph of the highly reduced highly defective graphene prepared in example 1;
FIG. 3 is an SEM image of a microwave-treated nickel oxide composite electrode material prepared in example 1;
fig. 4 is an SEM image of graphene oxide prepared in comparative example 1;
FIG. 5 is an XPS plot of graphite oxide prepared in comparative example 1;
FIG. 6 is an SEM image of a microwave-treated nickel oxide composite electrode material prepared in comparative example 1;
FIG. 7 is an SEM image of a microwave-treated nickel oxide composite electrode material prepared in comparative example 2;
FIG. 8 is a graph of constant current charge and discharge curves (GCD) at a current density of 1A/g for the nickel oxide composite electrode material before microwave treatment prepared in example 1;
FIG. 9 is a GCD plot of the microwave treated nickel oxide composite electrode material prepared in example 1at a current density of 1A/g;
FIG. 10 is a GCD plot of the nickel oxide composite electrode material prepared in comparative example 1 before microwave treatment at a current density of 1A/g;
FIG. 11 is a GCD plot of the microwave treated nickel oxide composite electrode material prepared in comparative example 1at a current density of 1A/g;
FIG. 12 is a GCD plot of the nickel oxide composite electrode material prepared in comparative example 2 before microwave treatment at a current density of 1A/g;
FIG. 13 is a GCD plot of the microwave treated nickel oxide composite electrode material prepared in comparative example 2at a current density of 1A/g;
FIG. 14 is a graph showing a comparison of specific capacitances of the nickel oxide composite electrode materials prepared in example 1, comparative example 1 and comparative example 2;
FIG. 15 is an Electrochemical Impedance Spectroscopy (EIS) graph of a microwave-treated nickel oxide composite electrode material prepared in example 1;
FIG. 16 is an EIS diagram of the microwave treated nickel oxide composite electrode material prepared in comparative example 1;
fig. 17 is an EIS diagram of the microwave-treated nickel oxide composite electrode material prepared in comparative example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting and the starting materials, reagents and equipment used are commercially available. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Firstly, preparing graphite oxide by a Hummers method in a chemical stripping method:
weighing 1g of scale graphite and 0.5g of sodium nitrate, placing the scale graphite and the sodium nitrate into a 250mL round-bottom flask, weighing 23mL of concentrated sulfuric acid with the weight percentage concentration of 98%, adding the concentrated sulfuric acid into the round-bottom flask, adding magnetons, placing the round-bottom flask into an ice-water bath, stirring for 30min, weighing 3g of potassium permanganate into a reactor, continuing to stir for 1H, after the reaction is finished, transferring the reactor into a 35 ℃ water bath, continuing to stir for 30min, weighing 50mL of distilled water, adding the distilled water into the round-bottom flask, transferring the round-bottom flask into a 98 ℃ oil bath, continuing to stir for 15min, sequentially adding 140mL of distilled water and 30% H by mass fraction into the round-bottom flask, and sequentially adding 140mL of distilled water and 30% H2O210mL, centrifuging after the reaction system finally becomes bright yellow, and washing with 500mL of hydrochloric acid with 5% of HCl in mass fraction and distilled water in sequence until the solution becomes neutral to prepare graphite oxide (with the oxygen atom content of 25-30 at.%) for later use;
secondly, reducing graphite oxide to prepare graphene:
loading the graphite oxide on the surface of a watch glass, drying to form a graphite oxide film with the thickness of 0.05mm, weighing 0.05g of the graphite oxide film, clamping the graphite oxide film by using tweezers, quickly approaching an alcohol lamp outer flame for 1s, and quickly reducing the graphite oxide film into black pre-reduced graphene oxide (with the oxygen atom content of 8-12 at.%) for later use.
Weighing 0.05g of the pre-reduced graphene oxide, placing the pre-reduced graphene oxide in a 100mL beaker, placing the beaker in a 1000W constant-power household microwave oven, and performing microwave treatment for 3s to obtain graphene (the oxygen atom content is 3.1-4 at.%) for later use;
step three, preparing the nickel oxide composite material:
weighing 10mg of graphene, placing the graphene in a 100mL beaker, adding 40mL of deionized water, carrying out ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl2·6H2And O, continuing ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 8h at the temperature of 140 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and drying in a 50 ℃ oven for 24h to obtain a nickel oxide composite material for later use;
fourthly, post-treatment of the nickel oxide composite material:
and weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the weighed material into a 100mL beaker, and placing the beaker into a 1000W constant-power household microwave oven for microwave treatment for 6 seconds to prepare the final nickel oxide composite material.
Example 2
Firstly, preparing graphite oxide by using a Standnmaier method in a chemical stripping method:
measuring 17.5mL of concentrated sulfuric acid and 9mL of concentrated nitric acid in a 250mL flask, and stirring for 15 min; weighing 1g of graphite, and slowly adding the graphite into a flask; after stirring evenly, 11g of potassium chlorate is added to react for 96 hours; washing with 800mL of distilled water, washing with 5% dilute hydrochloric acid, and finally washing with distilled water to neutrality to obtain graphite oxide (with oxygen atom content of 25-30 at.%) for later use;
secondly, reducing graphite oxide to prepare graphene:
loading the graphite oxide on the surface of a watch glass, drying to form a graphite oxide film with the thickness of 0.05mm, weighing 0.05g of the graphite oxide film, clamping the graphite oxide film by using tweezers, quickly approaching an alcohol lamp outer flame for 1s, and quickly reducing the graphite oxide film into black pre-reduced graphene oxide (with the oxygen atom content of 8-12 at.%) for later use.
Weighing 0.05g of the pre-reduced graphene oxide, placing the pre-reduced graphene oxide in a 100mL beaker, placing the beaker in a 1000W constant-power household microwave oven, and performing microwave treatment for 9s to obtain graphene (the oxygen atom content is 3.5-4.5 at.%) for later use;
step three, preparing the nickel oxide composite material:
weighing 10mg of graphene, placing the graphene in a 100mL beaker, adding 40mL of deionized water, carrying out ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl2·6H2And O, continuing ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 4h at the temperature of 180 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and drying in a 50 ℃ oven for 24h to obtain a nickel oxide composite material for later use;
fourthly, post-treatment of the nickel oxide composite material:
and (3) weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the weighed material into a 100mL beaker, and placing the beaker into a 1200W constant-power household microwave oven for microwave treatment for 3 seconds to prepare the final nickel oxide composite material.
Example 3
Firstly, preparing graphite oxide by a Hummers method in a chemical stripping method:
weighing 1g of scale graphite and 0.5g of sodium nitrate, placing the scale graphite and the sodium nitrate into a 250mL round-bottom flask, weighing 23mL of concentrated sulfuric acid with the weight percentage concentration of 98%, adding the concentrated sulfuric acid into the round-bottom flask, adding magnetons, placing the round-bottom flask into an ice-water bath, stirring for 30min, weighing 3g of potassium permanganate into a reactor, continuing to stir for 1H, after the reaction is finished, transferring the reactor into a 35 ℃ water bath, continuing to stir for 30min, weighing 50mL of distilled water, adding the distilled water into the round-bottom flask, transferring the round-bottom flask into a 98 ℃ oil bath, continuing to stir for 15min, sequentially adding 140mL of distilled water and 30% H by mass fraction into the round-bottom flask, and sequentially adding 140mL of distilled water and 30% H2O210mL, centrifuging after the reaction system finally becomes bright yellow, and washing with 500mL of hydrochloric acid with 5% of HCl in mass fraction and distilled water in sequence until the solution becomes neutral to prepare graphite oxide (with the oxygen atom content of 25-30 at.%) for later use;
secondly, reducing graphite oxide to prepare graphene:
loading the graphite oxide on the surface of a watch glass, drying to form a graphite oxide film with the thickness of 0.05mm, weighing 0.05g of the graphite oxide film, clamping the graphite oxide film by using a pair of tweezers, quickly approaching an outer flame of an alcohol lamp for 1s, and quickly reducing the graphite oxide film into black graphene (the oxygen atom content is 8-12 at.%) for later use;
step three, preparing the nickel oxide composite material:
weighing 10mg of graphene, placing the graphene in a 100mL beaker, adding 40mL of deionized water, carrying out ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl2·6H2And O, continuing to perform ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 12h at the temperature of 160 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and drying in a 50 ℃ oven for 24h to obtain a nickel oxide composite material for later use;
fourthly, post-treatment of the nickel oxide composite material:
and (3) weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the weighed material into a 100mL beaker, and placing the beaker into a 600W constant-power household microwave oven for microwave treatment for 15s to prepare the final nickel oxide composite material.
Example 4
Firstly, preparing graphite oxide by a Brodie method in a chemical stripping method:
2g of graphite powder was weighed and added to 3mL of a solution containing 3gK2S2O8And 3gP2O5Heating the graphite in concentrated sulfuric acid at the temperature of 80 ℃ for 6 hours, cooling the graphite to room temperature, diluting the graphite with distilled water, washing the graphite to be neutral, drying the graphite to obtain pre-oxidized graphite, weighing 1g of the obtained pre-oxidized graphite, adding the graphite into 46mL of concentrated sulfuric acid, adding 3g of potassium permanganate under the condition of ice-water bath, and reacting for 2 hours at the temperature of 35 ℃. Adding 46mL of distilled water after reaction, slowly adding 280mL of distilled water and 5mL of 30% hydrogen peroxide, centrifuging while hot, and finally washing with 500mL of 5% diluted hydrochloric acid and a large amount of distilled water to be neutral to obtain graphite oxide (with oxygen atom content of 25-30 at.%) for later use;
secondly, reducing graphite oxide to prepare graphene:
loading the graphite oxide on the surface of a watch glass, drying to form a graphite oxide film with the thickness of 0.05mm, weighing 0.05g of the graphite oxide film, clamping the graphite oxide film by using tweezers, quickly approaching an alcohol lamp outer flame for 1s, and quickly reducing the graphite oxide film into black pre-reduced graphene oxide (with the oxygen atom content of 8-12 at.%) for later use.
Weighing 0.05g of the pre-reduced graphene oxide, placing the pre-reduced graphene oxide in a 100mL beaker, placing the beaker in a 1000W constant-power household microwave oven, and performing microwave treatment for 6s to obtain graphene (the oxygen atom content is 4.5-5.5 at.%) for later use;
step three, preparing the nickel oxide composite material:
weighing 10mg of graphene, placing the graphene in a 100mL beaker, adding 40mL of deionized water, carrying out ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl2·6H2And O, continuing to perform ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 10h at the temperature of 150 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and drying in a 50 ℃ oven for 24h to obtain a nickel oxide composite material for later use;
fourthly, post-treatment of the nickel oxide composite material:
and weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the weighed material into a 100mL beaker, and placing the beaker into a 900W constant-power household microwave oven for microwave treatment for 8s to prepare the final nickel oxide composite material.
Example 5
Firstly, preparing graphite oxide by a Hummers method in a chemical stripping method:
weighing 1g of scale graphite and 0.5g of sodium nitrate, placing the scale graphite and the sodium nitrate into a 250mL round-bottom flask, weighing 23mL of concentrated sulfuric acid with the weight percentage concentration of 98%, adding the concentrated sulfuric acid into the round-bottom flask, adding magnetons, placing the round-bottom flask into an ice-water bath, stirring for 30min, weighing 3g of potassium permanganate into a reactor, continuing to stir for 1H, after the reaction is finished, transferring the reactor into a 35 ℃ water bath, continuing to stir for 30min, weighing 50mL of distilled water, adding the distilled water into the round-bottom flask, transferring the round-bottom flask into a 98 ℃ oil bath, continuing to stir for 15min, sequentially adding 140mL of distilled water and 30% H by mass fraction into the round-bottom flask, and sequentially adding 140mL of distilled water and 30% H2O210mL, centrifuging after the reaction system finally becomes bright yellow, and washing with 500mL of hydrochloric acid with 5% of HCl in mass fraction and distilled water in sequence until the solution becomes neutral to prepare graphite oxide (with the oxygen atom content of 25-30 at.%) for later use;
secondly, reducing graphite oxide to prepare graphene:
loading the graphite oxide on the surface of a watch glass, drying to form a graphite oxide film with the thickness of 0.05mm, weighing 0.05g of the graphite oxide film, clamping the graphite oxide film by using tweezers, quickly approaching an alcohol lamp outer flame for 1s, and quickly reducing the graphite oxide film into black pre-reduced graphene oxide (with the oxygen atom content of 8-12 at.%) for later use.
Weighing 0.05g of the pre-reduced graphene oxide, placing the pre-reduced graphene oxide in a 100mL beaker, placing the beaker in a 1000W constant-power household microwave oven, and performing microwave treatment for 4s to obtain graphene (the oxygen atom content is 3.2-4.1 at.%) for later use;
step three, preparing the nickel oxide composite material:
weighing 10mg of graphene, placing the graphene in a 100mL beaker, adding 40mL of deionized water, carrying out ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl2·6H2And O, continuing ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 6h at the temperature of 170 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and drying in a 50 ℃ oven for 24h to obtain a nickel oxide composite material for later use;
fourthly, post-treatment of the nickel oxide composite material:
and weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the weighed material into a 100mL beaker, and placing the beaker into an 800W constant-power household microwave oven for microwave treatment for 12s to prepare the final nickel oxide composite material.
Comparative example 1
Firstly, preparing graphite oxide by a Hummers method in a chemical stripping method:
weighing 1g of scale graphite and 0.5g of sodium nitrate, placing the scale graphite and the sodium nitrate into a 250mL round-bottom flask, weighing 23mL of concentrated sulfuric acid with the weight percentage concentration of 98%, adding the concentrated sulfuric acid into the round-bottom flask, adding magnetons, placing the round-bottom flask into an ice-water bath, stirring for 30min, weighing 3g of potassium permanganate, adding the potassium permanganate into a reactor, continuing to stir for 1h, after the reaction is finished, transferring the reactor into a 35 ℃ water bath, continuing to stir for 30min, weighing 50mL of distilled water, adding the distilled water into the round-bottom flask, continuing to stir for 50 minIn a bottle, the round bottom flask is transferred into an oil bath at the temperature of 98 ℃, stirring is continued for 15min, and 140mL of distilled water and 30 percent of H by mass are sequentially added2O210mL, centrifuging after the reaction system finally becomes bright yellow, and washing with 500mL of hydrochloric acid with 5% of HCl in mass fraction and distilled water in sequence until the solution becomes neutral to prepare graphite oxide (with the oxygen atom content of 25-30 at.%) for later use;
step two, preparing the nickel oxide composite material:
weighing 10mg of graphite oxide, placing the graphite oxide in a 100mL beaker, adding 40mL of deionized water, carrying out ultrasonic treatment for 30min, and then adding 40mg of urea and 40mg of NiCl2·6H2And O, continuing ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 8h at the temperature of 140 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and drying in a 50 ℃ oven for 24h to obtain a nickel oxide composite material for later use;
thirdly, post-treating the nickel oxide composite material:
and weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the weighed material into a 100mL beaker, and placing the beaker into a 1000W constant-power household microwave oven for microwave treatment for 6 seconds to prepare the final nickel oxide composite material.
Comparative example 2
Firstly, preparing graphite oxide by a Hummers method in a chemical stripping method:
weighing 1g of scale graphite and 0.5g of sodium nitrate, placing the scale graphite and the sodium nitrate into a 250mL round-bottom flask, weighing 23mL of concentrated sulfuric acid with the weight percentage concentration of 98%, adding the concentrated sulfuric acid into the round-bottom flask, adding magnetons, placing the round-bottom flask into an ice-water bath, stirring for 30min, weighing 3g of potassium permanganate into a reactor, continuing to stir for 1H, after the reaction is finished, transferring the reactor into a 35 ℃ water bath, continuing to stir for 30min, weighing 50mL of distilled water, adding the distilled water into the round-bottom flask, transferring the round-bottom flask into a 98 ℃ oil bath, continuing to stir for 15min, sequentially adding 140mL of distilled water and 30% H by mass fraction into the round-bottom flask, and sequentially adding 140mL of distilled water and 30% H2O210mL, after the reaction system finally turns to bright yellow, centrifuging, and then sequentially using 500mL of hydrochloric acid with the mass fraction of 5% HCl and distilled waterWashing until the solution becomes neutral to prepare graphite oxide (the oxygen atom content is 25-30 at.%) for later use;
step two, preparing the nickel oxide composite material:
weighing 10mg of graphite oxide, placing the graphite oxide in a 100mL beaker, adding 40mL of deionized water, carrying out ultrasonic treatment for 30min, and then adding 40mg of urea and 40mg of NiCl2·6H2And O, continuing ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 8h at 220 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and drying in a 50 ℃ oven for 24h to obtain a nickel oxide composite material for later use;
thirdly, post-treating the nickel oxide composite material:
and weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the weighed material into a 100mL beaker, and placing the beaker into a 1000W constant-power household microwave oven for microwave treatment for 6 seconds to prepare the final nickel oxide composite material.
Effects of the embodiment
(1) The nickel oxide composite electrode materials prepared in examples 1 to 5 and comparative examples 1 and 2 were subjected to specific capacitance and charge transfer resistance tests, respectively, and the results are shown in table 1.
(2) The assembly method of the working electrode in the three-electrode system comprises the following steps: 2mg of the nickel oxide composite electrode materials prepared in examples 1 to 5 and comparative examples 1 and 2 were uniformly loaded between two pieces of nickel foam, and pressed under a pressure of 8Mpa for 10min to prepare working electrodes.
(3) The counter electrode used in the three-electrode system is a platinum sheet electrode, the reference electrode used is a saturated calomel electrode, the electrolyte solution used is 2mol/L KOH aqueous solution, and the test equipment is Shanghai Hua 660E electrochemical workstation. The charge transfer impedance was obtained by an electrochemical impedance spectroscopy module (a.c. impedance) test in the shanghai hua 660E electrochemical workstation. Specific capacitance (C)s) Testing by a constant-current charge-discharge module (chronotropic measurement) in Shanghai Chenghua 660E electrochemical workstation by using a formula CsIt is calculated as It/m Δ v, and I, t, m, and v represent discharge current (a), discharge time(s), active material mass (g), and potential difference, respectively(V)。
TABLE 1
| Sample (I) | Charge transfer impedance (omega) | Specific capacitance (F/g) |
| Example 1 | 0.5～1 | 2300～2500 |
| Example 2 | 0.5～1 | 2100～2300 |
| Example 3 | 1～1.5 | 1500～1700 |
| Example 4 | 0.5～1 | 2200～2400 |
| Example 5 | 0.5～1 | 1900～2100 |
| Comparative example 1 | 9.5～11.5 | 750～850 |
| Comparative example 2 | 7～8.5 | 400～500 |
Examples and comparative examples will now be further illustrated with reference to the accompanying drawings:
fig. 1 is an SEM image of high-reduction high-defectivity graphene prepared in example 1; FIG. 2 is an XPS plot of the highly reduced highly defective graphene prepared in example 1; fig. 3 is an SEM image of the microwave-treated nickel oxide composite electrode material prepared in example 1. As can be seen from fig. 1, the highly reduced and highly defective graphene prepared in example 1 has a folded film-like structure, and this indicates that the graphene was successfully prepared. As can be seen from fig. 2, the high-reduction and high-defectivity graphene prepared in example 1 has a very low oxygen content, and the quantitative analysis shows that the oxygen content is only 3.5 at.%, which indicates that the high-reduction graphene is obtained after the reduction treatment. As can be seen from fig. 3, the nickel oxide composite electrode material prepared from example 1 exhibited a sheet-like structure.
Fig. 4 is an SEM image of graphene oxide prepared in comparative example 1; FIG. 5 is an XPS plot of graphite oxide prepared in comparative example 1; fig. 6 is an SEM image of the nickel oxide composite electrode material after microwave treatment prepared in comparative example 1. As can be seen from fig. 4, the graphene oxide prepared from comparative example 1 exhibited a wrinkled thin-film structure, and a significant discharge phenomenon occurred due to poor conductivity. As can be seen from fig. 5, the graphene oxide prepared from comparative example 1 contains a large amount of oxygen, and the oxygen content was found to be 28.3 at.% by quantitative analysis. As can be seen from fig. 6, the nickel oxide composite electrode material prepared from comparative example 1 also exhibited a sheet-like structure.
Fig. 7 is an SEM image of the microwave-treated nickel oxide composite electrode material prepared in comparative example 2. As can be seen from fig. 7, the nickel oxide composite electrode material prepared in comparative example 2 also exhibited a sheet-like structure.
FIG. 8 is a graph of the constant current charge-discharge curve (GCD) of the nickel oxide composite electrode material prepared in example 1 before microwave treatment; FIG. 9 is a GCD diagram of the microwave treated nickel oxide composite electrode material prepared in example 1. Comparing fig. 8 and fig. 9, it can be seen that the charging and discharging time of the nickel oxide composite electrode material prepared after the microwave treatment is significantly longer than that of the nickel oxide composite electrode material before the microwave treatment, which indicates that after the microwave treatment, the electrochemical activity of the nickel oxide composite electrode material is significantly improved, and a nickel oxide composite electrode material with high specific capacitance is obtained, which indicates that the electrochemical activity of the nickel oxide composite material can be effectively improved by modifying nickel oxide with high-reduction and high-defectivity graphene and then using the microwave treatment.
FIG. 10 is a GCD plot of a nickel oxide composite electrode material prepared in comparative example 1 before microwave treatment; fig. 11 is a GCD plot of a microwave treated nickel oxide composite electrode material prepared in comparative example 1. Comparing fig. 10 and fig. 11, it can be seen that the discharge time of the nickel oxide composite electrode material prepared after the microwave treatment is shorter than that of the nickel oxide composite electrode material before the microwave treatment, which indicates that the electrochemical activity of the nickel oxide composite electrode material is weakened after the microwave treatment, and the specific capacitance of the prepared nickel oxide composite electrode material is small, which indicates that modifying nickel oxide by using graphene oxide through hydrothermal reaction and then performing the microwave treatment is not favorable for obtaining a nickel oxide composite material with high activity
FIG. 12 is a GCD plot of a nickel oxide composite electrode material prepared in comparative example 2 before microwave treatment; fig. 13 is a GCD plot of a microwave treated nickel oxide composite electrode material prepared in comparative example 2. Comparing fig. 12 and fig. 13, it can be seen that the discharge time of the nickel oxide composite electrode material prepared after the microwave treatment is significantly longer than that of the nickel oxide composite electrode material before the microwave treatment, which indicates that the electrochemical activity of the nickel oxide composite electrode material is significantly improved after the microwave treatment, and the nickel oxide composite electrode material with high specific capacitance is obtained.
As is clear from example 1, comparative example 1, and comparative example 2, since example 1 and comparative example 2 can achieve a higher degree of reduction of graphene oxide, they are not only advantageous for microwave absorption and conversion into heat, but also can avoid the side effects caused by the gas generated by the decomposition of oxygen-containing functional groups in graphene, and thus a nickel oxide composite electrode material having higher activity is obtained after microwave treatment. Meanwhile, since the graphene with high reduction degree and high defect degree is obtained in the embodiment 1, the graphene can more effectively absorb microwaves and improve the activity of nickel oxide, so that the nickel oxide composite electrode material obtains the highest electrochemical activity.
Fig. 14 is a graph showing the specific capacitance comparison of the nickel oxide composite electrode materials prepared in example 1, comparative example 1, and comparative example 2, a being the specific capacitance of the microwave-treated nickel oxide composite electrode material prepared in comparative example 1, B being the specific capacitance of the microwave-treated nickel oxide composite electrode material prepared in comparative example 2, and C being the specific capacitance of the microwave-treated nickel oxide composite electrode material prepared in example 1. As can be seen from fig. 14, the specific capacitance of the nickel oxide composite electrode material prepared in example 1 is significantly higher than that of the nickel oxide composite electrode materials prepared in comparative examples 1 and 2.
FIG. 15 is an EIS diagram of a microwave treated nickel oxide composite electrode material prepared in example 1; FIG. 16 is an EIS diagram of a microwave-treated nickel oxide composite electrode material prepared in comparative example 1; fig. 17 is an EIS diagram of the nickel oxide composite electrode material after microwave treatment prepared in comparative example 2. As can be seen from fig. 15, the EIS diagram of the microwave-treated nickel oxide composite electrode material prepared in example 1 shows a negligible semicircle in the high frequency region, which indicates that the material has low charge transfer resistance and strong charge transfer capability, and is favorable for charge exchange of nickel oxide, thereby obtaining high electrochemical activity. As can be seen from fig. 16 and 17, the EIS diagrams of the microwave-treated nickel oxide composite electrode materials obtained in comparative examples 1 and 2 show a very distinct semicircle in the high frequency region, which indicates that the obtained nickel oxide composite electrode material has a large charge transfer resistance and a weak charge transfer capacity, and is not favorable for charge exchange of nickel oxide, so that high electrochemical activity cannot be obtained.
As can be seen from the attached figure of the detection results, the nickel oxide composite electrode material prepared by the method has high activity, high specific capacitance and good conductivity, and has great popularization value.
It should be understood that the examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that any changes and modifications to the present invention may occur to those skilled in the art after reading the present teachings, and such equivalents are also intended to be limited by the appended claims.
Claims (9)
1. A preparation method of a nickel oxide composite electrode material is characterized by comprising the following steps:
s1, preparation of graphite oxide: preparing graphite oxide for later use by using crystalline flake graphite as a precursor through a chemical stripping method;
s2, preparing graphene by reducing graphite oxide: taking graphite oxide, and carrying out reduction treatment on the graphite oxide to prepare graphene for later use;
s3, preparation of a nickel oxide composite material: taking graphene, urea and nickel chloride (NiCl)2·6H2O) is dispersed in water, and the nickel oxide/graphene composite material is prepared for standby through hydrothermal reaction;
s4, post-treatment of the nickel oxide composite material: and (3) performing microwave treatment on the nickel oxide/graphene composite material to prepare the nickel oxide composite electrode material.
2. The method for preparing a nickel oxide composite electrode material according to claim 1, wherein the chemical exfoliation method in step S1 includes Hummers method, Standenmaier method, Brodie method, and graphite oxide or graphene oxide is prepared by oxidation of flake graphite.
3. The method for producing a nickel oxide composite electrode material according to claim 2, wherein the graphite oxide produced in step S1 has an oxygen atom content of 25 to 30 at.%.
4. The method for preparing a nickel oxide composite electrode material according to claim 1, wherein the reduction treatment in the step S2 includes a flame method, a flame method and a microwave method, and the graphite oxide or the graphene oxide is reduced to obtain the highly-reduced highly-defective graphene.
5. The method for preparing a nickel oxide composite electrode material according to claim 4, wherein in the flame method + microwave method in the step S2, the microwave treatment time is 3-9S.
6. The method for preparing a nickel oxide composite electrode material according to claim 4, wherein the graphene prepared in step S2 has an oxygen atom content of 3.1 to 12 at.%.
7. The method for preparing a nickel hydroxide composite electrode material according to claim 1, wherein the graphene, the urea and the NiCl are obtained in step S32·6H2The mass ratio of O is 1: 4: 4.
8. the method for preparing the nickel oxide composite electrode material according to claim 7, wherein the hydrothermal reaction time in the step S3 is 4-12 h; the temperature of the hydrothermal reaction is 140-180 ℃.
9. The method for preparing a nickel oxide composite electrode material according to any one of claims 1 to 8, wherein the microwave treatment in step S4 is performed for 3 to 15 seconds; the power of the microwave treatment is 600-1200W.
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