Detailed Description
The invention is further illustrated by the following examples, but is not limited thereto, using commercially available raw materials, reagents and equipment. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
In the first step, graphite oxide is prepared by Hummers method in chemical exfoliation:
1g of crystalline flake graphite and 0.5g of sodium nitrate are weighed and placed in a 250mL round bottom flask, and the weight percentage concentration is measured to be 98%Adding 23mL of concentrated sulfuric acid into the round-bottom flask, adding a magneton, placing the round-bottom flask into an ice-water bath, stirring for 30min, weighing 3g of potassium permanganate, adding into a reactor, continuing stirring for 1H, transferring the reactor into a water bath kettle with the temperature of 35 ℃ after the reaction is completed, continuing stirring for 30min, weighing 50mL of distilled water, adding into the round-bottom flask, transferring the round-bottom flask into an oil bath with the temperature of 98 ℃, continuing stirring for 15min, and sequentially adding 140mL of distilled water and 30% of H by mass percent 2 O 2 After the reaction system finally turns into bright yellow, 10mL, centrifuging, and washing with 500mL of hydrochloric acid with 5% HCl 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, preparing graphene by reduction of graphite oxide:
and loading the graphite oxide on the surface of a surface dish, 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 forceps, quickly approaching to an alcohol lamp external 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, and placing the beaker in a 1000W constant-power household microwave oven for microwave treatment for 3s to obtain graphene (with the oxygen atom content of 3.1-4 at%), for later use;
thirdly, preparing a nickel oxide composite material:
weighing 10mg of graphene, placing in a 100mL beaker, adding 40mL of deionized water, performing ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl 2 ·6H 2 O, continuing ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 8h at 140 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and then placing the washed product in a 50 ℃ oven for drying for 24 hours to obtain a nickel oxide composite material for later use;
fourthly, post-treatment of the nickel oxide composite material:
weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the nickel oxide composite material in a 100mL beaker, and placing the beaker in a 1000W constant-power household microwave oven for microwave treatment for 6s to prepare the final nickel oxide composite material.
Example 2
In the first step, graphite oxide is prepared by a standby mail method in a chemical stripping method:
weighing 17.5mL of concentrated sulfuric acid and 9mL of concentrated nitric acid into a 250mL flask, and stirring for 15min; 1g of graphite was weighed and slowly added to the flask; after stirring evenly, adding 11g of potassium chlorate and reacting for 96 hours; washing with 800mL of distilled water, washing with 5% diluted 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, preparing graphene by reduction of graphite oxide:
and loading the graphite oxide on the surface of a surface dish, 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 forceps, quickly approaching to an alcohol lamp external 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, and placing the beaker in a 1000W constant-power household microwave oven for microwave treatment for 9s to obtain graphene (with the oxygen atom content of 3.5-4.5 at%), for later use;
thirdly, preparing a nickel oxide composite material:
weighing 10mg of graphene, placing in a 100mL beaker, adding 40mL of deionized water, performing ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl 2 ·6H 2 O, continuing ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 4h at 180 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and then placing the washed product in a 50 ℃ oven for drying for 24 hours to obtain a nickel oxide composite material for later use;
fourthly, post-treatment of the nickel oxide composite material:
weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the nickel oxide composite material in a 100mL beaker, and placing the beaker in a 1200W constant-power household microwave oven for microwave treatment for 3s to prepare the final nickel oxide composite material.
Example 3
In the first step, graphite oxide is prepared by Hummers method in chemical exfoliation:
1g of crystalline flake graphite and 0.5g of sodium nitrate are weighed and placed in a 250mL round-bottom flask, 23mL of concentrated sulfuric acid with the weight percentage concentration of 98% is weighed and added into the round-bottom flask, magneton is added, the round-bottom flask is placed in an ice-water bath and stirred for 30min, 3g of potassium permanganate is weighed and added into a reactor, the stirring is continued for 1H, after the reaction is completed, the reactor is transferred into a water bath kettle with the temperature of 35 ℃ and is continued to be stirred for 30min, 50mL of distilled water is measured and added into the round-bottom flask, then the round-bottom flask is transferred into an oil bath with the temperature of 98 ℃ and is continued to be stirred for 15min, and 140mL of distilled water and 30% of H with the weight percentage are sequentially added 2 O 2 After the reaction system finally turns into bright yellow, 10mL, centrifuging, and washing with 500mL of hydrochloric acid with 5% HCl 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, preparing graphene by reduction of graphite oxide:
loading the graphite oxide on the surface of a surface dish, 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 forceps, quickly approaching to an alcohol lamp external flame for 1s, and quickly reducing the graphite oxide film into black graphene (the oxygen atom content is 8-12 at%), for later use;
thirdly, preparing a nickel oxide composite material:
weighing 10mg of graphene, placing in a 100mL beaker, adding 40mL of deionized water, performing ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl 2 ·6H 2 O, continuing ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 12h at 160 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and then placing the washed product in a 50 ℃ oven for drying for 24 hours to obtain a nickel oxide composite material for later use;
fourthly, post-treatment of the nickel oxide composite material:
weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the nickel oxide composite material in a 100mL beaker, and placing the beaker in a 600W constant-power household microwave oven for microwave treatment for 15s to prepare the final nickel oxide composite material.
Example 4
In the first step, graphite oxide is prepared by a Brodie method in a chemical stripping method:
2g of graphite powder was weighed and added to 3mL containing 3gK 2 S 2 O 8 And 3gP 2 O 5 Heating at 80 ℃ for 6 hours, cooling to room temperature, diluting with distilled water, washing to neutrality, drying to obtain preoxidized graphite, weighing 1g of the obtained preoxidized graphite, adding into 46mL of concentrated sulfuric acid, adding 3g of potassium permanganate under the ice water bath condition, and reacting for 2 hours at 35 ℃. Adding 46mL of distilled water after the reaction, slowly adding 280mL of distilled water and 5mL of 30% hydrogen peroxide, centrifuging while the mixture is hot, and finally washing the mixture to be neutral by 500mL of 5% diluted hydrochloric acid and a large amount of distilled water to obtain graphite oxide (the oxygen atom content is 25-30 at.%) for later use;
secondly, preparing graphene by reduction of graphite oxide:
and loading the graphite oxide on the surface of a surface dish, 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 forceps, quickly approaching to an alcohol lamp external 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, and placing the beaker in a 1000W constant-power household microwave oven for microwave treatment for 6s to obtain graphene (with the oxygen atom content of 4.5-5.5 at%), for later use;
thirdly, preparing a nickel oxide composite material:
weighing 10mg of graphene, placing in a 100mL beaker, adding 40mL of deionized water, performing ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl 2 ·6H 2 O, continuing ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 10h at 150 ℃. The obtained product is treated with deionized water and ethanolRespectively washing for 5 times, and then drying in a drying oven at 50 ℃ for 24 hours to obtain a nickel oxide composite material for standby;
fourthly, post-treatment of the nickel oxide composite material:
weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the nickel oxide composite material in a 100mL beaker, and placing the beaker in a 900W constant-power household microwave oven for microwave treatment for 8s to prepare the final nickel oxide composite material.
Example 5
In the first step, graphite oxide is prepared by Hummers method in chemical exfoliation:
1g of crystalline flake graphite and 0.5g of sodium nitrate are weighed and placed in a 250mL round-bottom flask, 23mL of concentrated sulfuric acid with the weight percentage concentration of 98% is weighed and added into the round-bottom flask, magneton is added, the round-bottom flask is placed in an ice-water bath and stirred for 30min, 3g of potassium permanganate is weighed and added into a reactor, the stirring is continued for 1H, after the reaction is completed, the reactor is transferred into a water bath kettle with the temperature of 35 ℃ and is continued to be stirred for 30min, 50mL of distilled water is measured and added into the round-bottom flask, then the round-bottom flask is transferred into an oil bath with the temperature of 98 ℃ and is continued to be stirred for 15min, and 140mL of distilled water and 30% of H with the weight percentage are sequentially added 2 O 2 After the reaction system finally turns into bright yellow, 10mL, centrifuging, and washing with 500mL of hydrochloric acid with 5% HCl 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, preparing graphene by reduction of graphite oxide:
and loading the graphite oxide on the surface of a surface dish, 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 forceps, quickly approaching to an alcohol lamp external 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, and placing the beaker in a 1000W constant-power household microwave oven for microwave treatment for 4s to obtain graphene (with the oxygen atom content of 3.2-4.1 at%), for later use;
thirdly, preparing a nickel oxide composite material:
weighing 10mg of graphene, placing in a 100mL beaker, adding 40mL of deionized water, performing ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl 2 ·6H 2 O, continuing ultrasonic treatment for 15min, transferring the mixed solution into a 50ml hydrothermal reaction kettle, and reacting for 6h at 170 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and then placing the washed product in a 50 ℃ oven for drying for 24 hours to obtain a nickel oxide composite material for later use;
fourthly, post-treatment of the nickel oxide composite material:
weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the nickel oxide composite material in a 100mL beaker, and placing the beaker in a 800W constant-power household microwave oven for microwave treatment for 12s to prepare the final nickel oxide composite material.
Comparative example 1
In the first step, graphite oxide is prepared by Hummers method in chemical exfoliation:
1g of crystalline flake graphite and 0.5g of sodium nitrate are weighed and placed in a 250mL round-bottom flask, 23mL of concentrated sulfuric acid with the weight percentage concentration of 98% is weighed and added into the round-bottom flask, magneton is added, the round-bottom flask is placed in an ice-water bath and stirred for 30min, 3g of potassium permanganate is weighed and added into a reactor, the stirring is continued for 1H, after the reaction is completed, the reactor is transferred into a water bath kettle with the temperature of 35 ℃ and is continued to be stirred for 30min, 50mL of distilled water is measured and added into the round-bottom flask, then the round-bottom flask is transferred into an oil bath with the temperature of 98 ℃ and is continued to be stirred for 15min, and 140mL of distilled water and 30% of H with the weight percentage are sequentially added 2 O 2 After the reaction system finally turns into bright yellow, 10mL, centrifuging, and washing with 500mL of hydrochloric acid with 5% HCl 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, preparing a nickel oxide composite material:
weighing 10mg of graphite oxide, placing in a 100mL beaker, adding 40mL of deionized water, performing ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl 2 ·6H 2 O, continuing to carry out ultrasonic treatment for 15min, and transferring the mixed solution toIn a 50ml hydrothermal reaction kettle, the reaction is carried out for 8 hours at 140 ℃. Washing the obtained product with deionized water and ethanol for 5 times respectively, and then placing the washed product in a 50 ℃ oven for drying for 24 hours to obtain a nickel oxide composite material for later use;
thirdly, post-treatment of the nickel oxide composite material:
weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the nickel oxide composite material in a 100mL beaker, and placing the beaker in a 1000W constant-power household microwave oven for microwave treatment for 6s to prepare the final nickel oxide composite material.
Comparative example 2
In the first step, graphite oxide is prepared by Hummers method in chemical exfoliation:
1g of crystalline flake graphite and 0.5g of sodium nitrate are weighed and placed in a 250mL round-bottom flask, 23mL of concentrated sulfuric acid with the weight percentage concentration of 98% is weighed and added into the round-bottom flask, magneton is added, the round-bottom flask is placed in an ice-water bath and stirred for 30min, 3g of potassium permanganate is weighed and added into a reactor, the stirring is continued for 1H, after the reaction is completed, the reactor is transferred into a water bath kettle with the temperature of 35 ℃ and is continued to be stirred for 30min, 50mL of distilled water is measured and added into the round-bottom flask, then the round-bottom flask is transferred into an oil bath with the temperature of 98 ℃ and is continued to be stirred for 15min, and 140mL of distilled water and 30% of H with the weight percentage are sequentially added 2 O 2 After the reaction system finally turns into bright yellow, 10mL, centrifuging, and washing with 500mL of hydrochloric acid with 5% HCl 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, preparing a nickel oxide composite material:
weighing 10mg of graphite oxide, placing in a 100mL beaker, adding 40mL of deionized water, performing ultrasonic treatment for 30min, and adding 40mg of urea and 40mg of NiCl 2 ·6H 2 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 then placing the washed product in a 50 ℃ oven for drying for 24 hours to obtain a nickel oxide composite material for later use;
thirdly, post-treatment of the nickel oxide composite material:
weighing 0.05g of the nickel oxide composite material prepared in the third step, placing the nickel oxide composite material in a 100mL beaker, and placing the beaker in a 1000W constant-power household microwave oven for microwave treatment for 6s to prepare the final nickel oxide composite material.
Effects of the examples
(1) The nickel oxide composite electrode materials prepared in examples 1 to 5 and comparative examples 1 and 2 were respectively tested for specific capacitance and charge transfer resistance, and the results are shown in table 1.
(2) The method for assembling 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, respectively, were uniformly supported between two sheets of foamed nickel, 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 a 2mol/L KOH aqueous solution, and the testing equipment is an Shanghai Chenhua 660E electrochemical workstation. The charge transfer impedance was obtained by an electrochemical impedance spectroscopy module (a.c. impedance) test in the Shanghai Chenhua 660E electrochemical workstation. Specific capacitance (C) s ) Through a constant current charge-discharge module (chronocentiometry) test in an Shanghai Chen Hua 660E electrochemical workstation, and using a formula C s Calculated by It/mΔv, I, t, m, V represents discharge current (a), discharge time(s), active mass (g), and potential difference (V), respectively.
TABLE 1
Sample of
|
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 described with reference to the accompanying drawings:
fig. 1 is an SEM image of high reduction degree high defect degree graphene prepared in example 1; fig. 2 is an XPS diagram of high reduction degree and high defect degree graphene prepared in example 1; fig. 3 is an SEM image of the nickel oxide composite electrode material after microwave treatment prepared in example 1. As can be seen from fig. 1, the high-reduction-degree high-defect-degree graphene prepared in example 1 has a wrinkled film-like structure, which indicates that graphene was successfully prepared. As can be seen from fig. 2, the high-reduction-degree high-defect-degree graphene prepared in example 1 has very low oxygen content, and the oxygen content is only 3.5at.% through quantitative analysis, which indicates that the high-reduction-degree graphene is obtained after reduction treatment. As can be seen from fig. 3, the nickel oxide composite electrode material prepared in example 1 exhibits a sheet-like structure.
FIG. 4 is an SEM image of graphene oxide prepared in comparative example 1; FIG. 5 is an XPS chart 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 in comparative example 1 exhibits a wrinkled film-like structure, and a significant discharge phenomenon occurs due to poor conductivity. As can be seen from fig. 5, the graphene oxide prepared in comparative example 1 contains a large amount of oxygen, and the oxygen content was found to be 28.3at.% by quantitative analysis. As can be seen from fig. 6, the nickel oxide composite electrode material prepared in comparative example 1 also exhibits a sheet-like structure.
Fig. 7 is an SEM image of the nickel oxide composite electrode material after microwave treatment prepared in comparative example 2. As can be seen from fig. 7, the nickel oxide composite electrode material prepared in comparative example 2 also exhibits a sheet-like structure.
FIG. 8 is a graph showing 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 nickel oxide composite electrode material after microwave treatment obtained in example 1. Comparing fig. 8 and fig. 9, it can be seen that the charge-discharge time of the nickel oxide composite electrode material prepared after microwave treatment is significantly longer than that of the nickel oxide composite electrode material before microwave treatment, which means that the electrochemical activity of the nickel oxide composite electrode material is significantly improved after microwave treatment, and the 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 using graphene modified nickel oxide with high reduction degree and high defect degree to reuse microwave treatment.
FIG. 10 is a GCD diagram of a nickel oxide composite electrode material prepared in comparative example 1 before microwave treatment; FIG. 11 is a GCD diagram of a nickel oxide composite electrode material after microwave treatment prepared in comparative example 1. Comparing fig. 10 and 11, it can be seen that the discharge time of the nickel oxide composite electrode material obtained after microwave treatment is shorter than that of the nickel oxide composite electrode material before microwave treatment, which indicates that the electrochemical activity of the nickel oxide composite electrode material is weakened after microwave treatment, and the specific capacitance of the nickel oxide composite electrode material is small, which indicates that modification of nickel oxide by using graphene oxide through hydrothermal reaction and further microwave treatment are unfavorable for obtaining the nickel oxide composite material with high activity
FIG. 12 is a GCD diagram of a nickel oxide composite electrode material prepared in comparative example 2 before microwave treatment; FIG. 13 is a GCD diagram of a nickel oxide composite electrode material after microwave treatment 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 by microwave treatment is significantly longer than that of the nickel oxide composite electrode material before microwave treatment, which means that the electrochemical activity of the nickel oxide composite electrode material is significantly improved after microwave treatment, and the nickel oxide composite electrode material with high specific capacitance is obtained.
As can be seen from example 1, comparative example 1 and comparative example 2, since example 1 and comparative example 2 can achieve a higher reduction degree of graphene oxide, not only is the conversion of microwave absorption into heat facilitated, but also side effects caused by gas generated by decomposition of oxygen-containing functional groups in graphene can be avoided, and thus a nickel oxide composite electrode material with higher activity is obtained after microwave treatment. Meanwhile, as the graphene with high reduction degree and high defect degree is obtained in the embodiment 1, the graphene can absorb microwaves more effectively and improve the activity of nickel oxide, so that the nickel oxide composite electrode material obtains the highest electrochemical activity.
Fig. 14 is a comparative graph of specific capacitances of the nickel oxide composite electrode materials prepared in example 1, comparative example 1, and comparative example 2, a is a specific capacitance of the nickel oxide composite electrode material after microwave treatment prepared in comparative example 1, B is a specific capacitance of the nickel oxide composite electrode material after microwave treatment prepared in comparative example 2, and C is a specific capacitance of the nickel oxide composite electrode material after microwave treatment 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 the nickel oxide composite electrode material after microwave treatment obtained in example 1; FIG. 16 is an EIS diagram of the nickel oxide composite electrode material after microwave treatment obtained in comparative example 1; FIG. 17 is an EIS diagram of the nickel oxide composite electrode material after microwave treatment obtained in comparative example 2. As can be seen from fig. 15, the EIS diagram of the nickel oxide composite electrode material after microwave treatment prepared in example 1 shows a negligible semicircle in the high frequency region, which indicates that the charge transfer resistance is small, the charge transfer capability is strong, and the nickel oxide is favorable for charge exchange, thereby obtaining high electrochemical activity. As can be seen from fig. 16 and 17, the EIS diagrams of the nickel oxide composite electrode materials obtained in comparative examples 1 and 2 after the microwave treatment show a very obvious semicircle in the high frequency region, which indicates that the obtained nickel oxide composite electrode material has large charge transfer resistance and weak charge transfer capability, and is unfavorable for the charge exchange of nickel oxide, so that high electrochemical activity cannot be obtained.
As can be seen from the above detection results, the nickel oxide composite electrode material prepared by the invention has high activity, high specific capacitance and good conductivity, and has great popularization value.
It is to be understood that the examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Furthermore, it should be understood that after reading the teachings of the present invention, those skilled in the art may make any of various changes and modifications to the present invention, and that such equivalents will likewise fall within the limitations of the claims appended hereto.