CN109360739B - Preparation method of nickel/nickel oxide loaded carbon nanofiber electrode material - Google Patents

Preparation method of nickel/nickel oxide loaded carbon nanofiber electrode material Download PDF

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CN109360739B
CN109360739B CN201811543568.2A CN201811543568A CN109360739B CN 109360739 B CN109360739 B CN 109360739B CN 201811543568 A CN201811543568 A CN 201811543568A CN 109360739 B CN109360739 B CN 109360739B
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wood fiber
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carbon nanofiber
electrode material
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吴义强
卿彦
李蕾
罗莎
刘明
张振
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Central South University of Forestry and Technology
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Abstract

The invention discloses a preparation method of a nickel/nickel oxide loaded carbon nanofiber electrode material, which comprises the following steps: (1) dispersing the nano wood fiber in ultrapure water, carrying out vacuum filtration, and drying to obtain a nano wood fiber film; (2) soaking the nano wood fiber film obtained in the step (1) in a nickel salt solution, taking out and drying the nano wood fiber film, and then carrying out high-temperature carbonization treatment to obtain a nickel/carbon nano fiber film material; (3) and (3) carrying out electro-oxidation treatment on the nickel/carbon nanofiber thin film material obtained in the step (2) to obtain the nickel/nickel oxide loaded carbon nanofiber electrode material. According to the invention, the nickel oxide and the carbon nanofiber are combined, and the excellent performances of the nickel oxide and the carbon nanofiber are combined, so that the use limitation of a single electrode material is made up, and the electrochemical performance of the electrode material is greatly improved.

Description

Preparation method of nickel/nickel oxide loaded carbon nanofiber electrode material
Technical Field
The invention belongs to the field of energy storage materials, and particularly relates to a preparation method of an electrode.
Background
An energy storage device is a device that can achieve energy conversion and storage. With the continuous development of the modernization process, the demand of the energy storage device is increasing, and therefore, the development of the energy storage device with high performance is urgently needed. Energy storage devices are generally classified into two categories, namely batteries and capacitors, wherein the batteries have high energy density and low power density, and the capacitors have opposite energy density and low power density. The above differences mainly depend on the energy storage mechanism of the energy storage device, which is closely related to the electrode material.
Electrode materials are important components of energy storage devices, and commonly used electrode materials are mainly transition metal oxides such as nickel oxide, ruthenium oxide, cobalt oxide and the like, and carbon materials such as graphene, carbon nanotubes, activated carbon and the like. The metal oxide has higher theoretical capacity, but the problems of poor conductivity, smaller specific surface area, narrower voltage range and the like limit the further development of the metal oxide in the energy storage material. Carbon materials have good electrical conductivity and a wide voltage window, but have a low theoretical capacity and a high contact resistance.
In order to solve the disadvantages of the above materials, a composite method can be adopted to combine the metal oxide and the carbon material to obtain the advantages of the metal oxide and the carbon material at the same time. However, in the existing method for preparing the electrode, the active material, the binder, the conductive agent and the like are mixed to prepare slurry, and then the slurry is coated on the current collector, wherein the addition of the binder and the conductive agent greatly influences the resistance and the wettability of the electrode material, so that the conductivity and the capacitance performance of the electrode are influenced.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings mentioned in the background technology, and provide a preparation method of a nickel/nickel oxide loaded carbon nanofiber electrode material with excellent conductivity and capacitance. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a nickel/nickel oxide loaded carbon nanofiber electrode material comprises the following steps:
(1) dispersing the nano wood fiber in ultrapure water, carrying out vacuum filtration, and drying to obtain a nano wood fiber film; the nano wood fiber has good film forming property, the fiber is self-assembled into a film due to the weight loss of the drained water in the suction filtration process, and a flexible film can be obtained after drying;
(2) soaking the nano wood fiber film obtained in the step (1) in a nickel salt solution, taking out and drying the nano wood fiber film, and then carrying out high-temperature carbonization treatment to obtain a nickel/carbon nano fiber film material; during high-temperature carbonization, nickel ions can be reduced into a nickel simple substance;
(3) carrying out electro-oxidation treatment on the nickel/carbon nanofiber thin film material obtained in the step (2) to obtain a nickel/nickel oxide loaded carbon nanofiber electrode material; the function of the electro-oxidation treatment is to oxidize the elementary nickel into nickel oxide, thereby increasing the capacitance performance of the material.
In the preparation method, the nano wood fiber needs to be prepared into a film form and then soaked in the nickel salt solution, if the nano wood fiber is soaked in the nickel ion adsorption solution, the nickel ion is difficult to adhere to the nano wood fiber and form a film in a suction filtration form, because the nickel ion is dissolved in water, the nickel ion is easy to be pumped away with the water in the suction filtration process, and even if partial nickel ion adsorption exists, the distribution is uneven. Experimental research shows that the adsorption after film formation can solve the problems of uneven adsorption, low load capacity and the like, and the method is simple and easy to implement.
In the above preparation method, preferably, the nano wood fiber is prepared from cellulose powder by acid hydrolysis-high pressure homogenization; the nickel salt in the nickel salt solution is at least one of nickel chloride hexahydrate, nickel sulfate hexahydrate or nickel nitrate hexahydrate.
In the above preparation method, the mass of the nickel salt supported on the nano wood fiber film during soaking in the step (2) is preferably controlled to be 10% to 70% of the total mass of the nickel/carbon nano fiber film material, and more preferably 30% to 60%. The loading amount of the nickel salt has a great influence on the performance of subsequent electrode materials, the loading amount of the nickel salt needs to be controlled to be more preferably 30-60%, and the electrochemical performance of the electrode material is optimal.
In the above preparation method, it is preferable that the mass concentration of the nano wood fiber solution is controlled to 0.5 to 0.8wt.% when the nano wood fiber is dispersed in ultrapure water. The mass concentration of the nano wood fiber has great influence on the porosity of the formed film, and the control of the mass concentration and the control of high-temperature carbonization are mutually matched, so that the electrode material with the optimal electrochemical performance can be obtained.
In the preparation method, preferably, the high-temperature carbonization treatment is carried out in a tubular furnace under the protection of nitrogen, the carbonization temperature is kept at 1000 ℃, the temperature rise rate is 5-10 ℃/min, and the heat preservation time is 1-3 h. The technological parameters of the carbonization treatment have certain influence on the pore result of the electrode material, and the determination of the high-temperature carbonization temperature is favorable for obtaining the electrode material with excellent electrochemical performance.
In the preparation method, preferably, the electro-oxidation treatment is to place the nickel/carbon nanofiber thin film material in a three-electrode system and then treat the nickel/carbon nanofiber thin film material by a potentiostatic method, wherein the electrolyte is potassium hydroxide solution (1mol/L or 6mol/L) during treatment, the control voltage is 0.8-1.2V, and the sensitivity (sensitivity) is set to 1.0e-1The treatment time is 30-600s (more preferably 300-600 s). The control of the technological parameters of the electro-oxidation treatment has great influence on the electrode performance, and the control of the parameters of the electro-oxidation treatment can control the mass ratio of the simple substance nickel, the nickel oxide and the nano wood fiber, thereby regulating and controlling the best electrochemical performance.
The electrode material prepared by the invention can uniformly load nickel and nickel oxide on the carbon nanofiber, the carbon nanofiber has certain strength and conductivity, the conductivity of the electrode material is improved, a framework and a supporting system can be provided for the nickel oxide, the oxide is not easy to agglomerate in the forming process, a nano structure can be formed, and the advantages of the nickel oxide and the carbon are compounded by the thin film electrode material. In addition, the electrode material is in a film form, can be directly used as an electrode, and can save links such as grinding, pulping and the like.
When the electrode is prepared, the shape and the performance of the electrode material can be regulated and controlled by jointly regulating and controlling the mass ratio of the nano wood fiber to the nickel salt, the concentration (water content) of the nano wood fiber, the electrooxidation treatment process and the like so as to obtain the optimal electrochemical effect.
The electrode prepared by the method can be used as an electrode material of a battery, such as a lithium ion battery and a nickel-zinc battery, and can also be used as an electrode material of a capacitor, such as an asymmetric super capacitor.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the nickel oxide and the carbon nanofiber are combined, and the excellent performances of the nickel oxide and the carbon nanofiber are combined, so that the use limitation of a single electrode material is made up, and the electrochemical performance of the electrode material is greatly improved.
2. When the electrode material is prepared, electrode slurry does not need to be prepared, the use of the binder and the conductive agent is reduced, the influence of the addition of the binder and the conductive agent on the resistance and the wettability of the electrode material is avoided, and the electrode material has excellent conductivity and capacitance.
3. The electrode material is in a film form and can be directly used as an electrode.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic flow chart of a preparation method in an embodiment of the present invention.
FIG. 2 is a macroscopic view of the electrode material prepared in example 1 (in the figure, a is a nano wood fiber film, and b is a nickel/carbon nano fiber film material).
Fig. 3 is an SEM image of the electrode material prepared in example 1.
Fig. 4 is an ac impedance diagram of the electrode material prepared in example 1.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
as shown in fig. 1, a method for preparing a nickel/nickel oxide-loaded carbon nanofiber electrode material comprises the following steps:
(1) dispersing 50g of nano wood fiber (prepared from cellulose powder by an acid hydrolysis-high pressure homogenization method) in ultrapure water (the mass concentration of the nano wood fiber is controlled to be 0.5 wt.%), carrying out vacuum filtration, naturally drying, and removing a filter membrane to obtain a transparent nano wood fiber film;
(2) soaking the nano wood fiber film obtained in the step (1) in a nickel sulfate hexahydrate solution of 1mol/L, taking out and naturally drying, and controlling the nickel salt loading to be 60% of the total mass of the nano wood fiber film (including the mass of the nickel salt and the nano wood fiber film, the same below). Then carrying out high-temperature carbonization treatment in a tubular furnace to obtain a nickel/carbon nanofiber film material; wherein the carbonization temperature is controlled to be 700 ℃, the heating rate is 5 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection;
(3) placing the nickel/carbon nanofiber membrane material obtained in the step (2) in a three-electrode electrolytic cell for potentiostatic treatment, and then cleaning with ethanol and ultrapure water to obtain a nickel/nickel oxide-loaded carbon nanofiber electrode material; wherein the electrolyte in the electrolytic cell adopts 6mol/L potassium hydroxide, the control voltage is 1V, the sensitivity is set to be 1.0e-1The treatment time was 600 s.
The macroscopic view of the electrode material prepared in this example is shown in fig. 2, and it is known that the nano wood fiber film can still maintain a film-like structure after absorbing nickel salt and carbonizing. The SEM image of the electrode material prepared in this example is shown in fig. 3, and it can be seen that nano nickel oxide is uniformly attached to the surface of the carbon nanofiber. When the electrochemical performance of the electrode material is tested, the alternating current impedance is shown in fig. 4, and the electrode material has a low resistance value of 2.5 omega and good conductivity. The electrochemical performance of the electrode material in the embodiment is better, and the specific capacitance of the prepared electrode material is 116F/g.
Example 2:
as shown in fig. 1, a method for preparing a nickel/nickel oxide-loaded carbon nanofiber electrode material comprises the following steps:
(1) dispersing 50g of nano wood fiber (prepared from cellulose powder by an acid hydrolysis-high pressure homogenization method) in ultrapure water (the mass concentration of the nano wood fiber is controlled to be 0.5 wt.%), carrying out vacuum filtration, naturally drying, and removing a filter membrane to obtain a transparent nano wood fiber film;
(2) soaking the nano wood fiber film obtained in the step (1) in a nickel sulfate hexahydrate solution of 1mol/L, taking out and naturally drying, and controlling the nickel salt loading to be 60% of the total mass of the nano wood fiber film. Then carrying out high-temperature carbonization treatment in a tubular furnace to obtain a nickel/carbon nanofiber film material; wherein the carbonization temperature is controlled to be 800 ℃, the heating rate is 5 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection;
(3) placing the nickel/carbon nanofiber membrane material obtained in the step (2) in a three-electrode electrolytic cell for potentiostatic treatment, and then cleaning with ethanol and ultrapure water to obtain a nickel/nickel oxide-loaded carbon nanofiber electrode material; wherein the electrolyte in the electrolytic cell adopts 6mol/L potassium hydroxide, the control voltage is 1V, the sensitivity is set to be 1.0e-1The treatment time was 100 s.
The electrode material prepared in this example had a low resistance of 1 Ω and a specific capacitance of 80F/g.
Example 3:
as shown in fig. 1, a method for preparing a nickel/nickel oxide-loaded carbon nanofiber electrode material comprises the following steps:
(1) dispersing 50g of nano wood fiber (prepared from cellulose powder by an acid hydrolysis-high pressure homogenization method) in ultrapure water (the mass concentration of the nano wood fiber is controlled to be 0.5 wt.%), carrying out vacuum filtration, naturally drying, and removing a filter membrane to obtain a transparent nano wood fiber film;
(2) soaking the nano wood fiber film obtained in the step (1) in 1mol/L nickel chloride hexahydrate solution, taking out and naturally drying, and controlling the nickel salt loading to be 10% of the total mass of the nano wood fiber film. Then carrying out high-temperature carbonization treatment in a tubular furnace to obtain a nickel/carbon nanofiber film material; wherein the carbonization temperature is controlled to be 800 ℃, the heating rate is 5 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection;
(3) placing the nickel/carbon nanofiber membrane material obtained in the step (2) in a three-electrode electrolytic cell for potentiostatic treatment, and then cleaning with ethanol and ultrapure water to obtain a nickel/nickel oxide-loaded carbon nanofiber electrode material; wherein the electrolyte in the electrolytic cell adopts 6mol/L potassium hydroxide, the control voltage is 1V, the sensitivity is set to be 1.0e-1The treatment time was 400 s.
The electrode material prepared in this example had a low resistance of 1.5 Ω and a specific capacitance of 40F/g.
Example 4:
as shown in fig. 1, a method for preparing a nickel/nickel oxide-loaded carbon nanofiber electrode material comprises the following steps:
(1) dispersing 50g of nano wood fiber (prepared from cellulose powder by an acid hydrolysis-high pressure homogenization method) in ultrapure water (the mass concentration of the nano wood fiber is controlled to be 0.5 wt.%), carrying out vacuum filtration, naturally drying, and removing a filter membrane to obtain a transparent nano wood fiber film;
(2) soaking the nano wood fiber film obtained in the step (1) in 5mol/L nickel chloride hexahydrate solution, taking out and naturally drying, and controlling the nickel salt loading to be 30% of the total mass of the nano wood fiber film. Then carrying out high-temperature carbonization treatment in a tubular furnace to obtain a nickel/carbon nanofiber film material; wherein the carbonization temperature is controlled to be 1000 ℃, the heating rate is 5 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection;
(3) the nickel/carbon nano-particles obtained in the step (2)Placing the fiber film material in a three-electrode electrolytic tank for potentiostatic treatment, and then cleaning with ethanol and ultrapure water to obtain the nickel/nickel oxide loaded carbon nanofiber electrode material; wherein the electrolyte in the electrolytic cell adopts 6mol/L potassium hydroxide, the control voltage is 1V, the sensitivity is set to be 1.0e-1The treatment time was 100 s.
The electrode material prepared in this example had a low resistance of 1 Ω and a specific capacitance of 20F/g.
Example 5:
as shown in fig. 1, a method for preparing a nickel/nickel oxide-loaded carbon nanofiber electrode material comprises the following steps:
(1) dispersing 50g of nano wood fiber (prepared from cellulose powder by an acid hydrolysis-high pressure homogenization method) in ultrapure water (the mass concentration of the nano wood fiber is controlled to be 0.5 wt.%), carrying out vacuum filtration, naturally drying, and removing a filter membrane to obtain a transparent nano wood fiber film;
(2) soaking the nano wood fiber film obtained in the step (1) in 5mol/L nickel chloride hexahydrate solution, taking out and naturally drying, and controlling the nickel salt loading to be 48% of the total mass of the nano wood fiber film. Then carrying out high-temperature carbonization treatment in a tubular furnace to obtain a nickel/carbon nanofiber film material; wherein the carbonization temperature is controlled to be 700 ℃, the heating rate is 5 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection;
(3) placing the nickel/carbon nanofiber membrane material obtained in the step (2) in a three-electrode electrolytic cell for potentiostatic treatment, and then cleaning with ethanol and ultrapure water to obtain a nickel/nickel oxide-loaded carbon nanofiber electrode material; wherein the electrolyte in the electrolytic cell adopts 6mol/L potassium hydroxide, the control voltage is 1V, the sensitivity is set to be 1.0e-1The treatment time was 450 s.
The electrode material prepared in this example had a low resistance of 0.9 Ω and a specific capacitance of 125F/g.
Example 6:
as shown in fig. 1, a method for preparing a nickel/nickel oxide-loaded carbon nanofiber electrode material comprises the following steps:
(1) dispersing 50g of nano wood fiber (prepared from cellulose powder by an acid hydrolysis-high pressure homogenization method) in ultrapure water (the mass concentration of the nano wood fiber is controlled to be 0.5 wt.%), carrying out vacuum filtration, naturally drying, and removing a filter membrane to obtain a transparent nano wood fiber film;
(2) soaking the nano wood fiber film obtained in the step (1) in 5mol/L nickel chloride hexahydrate solution, taking out and naturally drying, and controlling the nickel salt loading to be 55% of the total mass of the nano wood fiber film. Then carrying out high-temperature carbonization treatment in a tubular furnace to obtain a nickel/carbon nanofiber film material; wherein the carbonization temperature is controlled to be 700 ℃, the heating rate is 5 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection;
(3) placing the nickel/carbon nanofiber membrane material obtained in the step (2) in a three-electrode electrolytic cell for potentiostatic treatment, and then cleaning with ethanol and ultrapure water to obtain a nickel/nickel oxide-loaded carbon nanofiber electrode material; wherein the electrolyte in the electrolytic cell adopts 6mol/L potassium hydroxide, the control voltage is 1V, the sensitivity is set to be 1.0e-1The treatment time was 450 s.
The electrode material prepared in this example had a low resistance of 1 Ω and a specific capacitance of 112F/g.
Example 7:
as shown in fig. 1, a method for preparing a nickel/nickel oxide-loaded carbon nanofiber electrode material comprises the following steps:
(1) dispersing 50g of nano wood fiber (prepared from cellulose powder by an acid hydrolysis-high pressure homogenization method) in ultrapure water (the mass concentration of the nano wood fiber is controlled to be 0.5 wt.%), carrying out vacuum filtration, naturally drying, and removing a filter membrane to obtain a transparent nano wood fiber film;
(2) soaking the nano wood fiber film obtained in the step (1) in 5mol/L nickel chloride hexahydrate solution, taking out and naturally drying, and controlling the nickel salt loading to be 40% of the total mass of the nano wood fiber film. Then carrying out high-temperature carbonization treatment in a tubular furnace to obtain a nickel/carbon nanofiber film material; wherein the carbonization temperature is controlled to be 700 ℃, the heating rate is 5 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection;
(3) placing the nickel/carbon nanofiber membrane material obtained in the step (2) in a three-electrode electrolytic cell for potentiostatic treatment, and then cleaning with ethanol and ultrapure water to obtain a nickel/nickel oxide-loaded carbon nanofiber electrode material; wherein the electrolyte in the electrolytic cell adopts 6mol/L potassium hydroxide, the control voltage is 1V, the sensitivity is set to be 1.0e-1The treatment time was 450 s.
The electrode material prepared in this example had a low resistance of 1 Ω and a specific capacitance of 100F/g.
Example 8:
as shown in fig. 1, a method for preparing a nickel/nickel oxide-loaded carbon nanofiber electrode material comprises the following steps:
(1) dispersing 50g of nano wood fiber (prepared from cellulose powder by an acid hydrolysis-high pressure homogenization method) in ultrapure water (the mass concentration of the nano wood fiber is controlled to be 0.5 wt.%), carrying out vacuum filtration, naturally drying, and removing a filter membrane to obtain a transparent nano wood fiber film;
(2) soaking the nano wood fiber film obtained in the step (1) in 5mol/L nickel chloride hexahydrate solution, taking out and naturally drying, and controlling the nickel salt loading to be 48% of the total mass of the nano wood fiber film. Then carrying out high-temperature carbonization treatment in a tubular furnace to obtain a nickel/carbon nanofiber film material; wherein the carbonization temperature is controlled to be 700 ℃, the heating rate is 5 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection;
(3) placing the nickel/carbon nanofiber membrane material obtained in the step (2) in a three-electrode electrolytic cell for potentiostatic treatment, and then cleaning with ethanol and ultrapure water to obtain a nickel/nickel oxide-loaded carbon nanofiber electrode material; wherein the electrolyte in the electrolytic cell adopts 6mol/L potassium hydroxide, the control voltage is 1V, the sensitivity is set to be 1.0e-1The treatment time was 550 s.
The electrode material prepared in this example had a low resistance of 1.1 Ω and a specific capacitance of 120F/g.
Example 9:
as shown in fig. 1, a method for preparing a nickel/nickel oxide-loaded carbon nanofiber electrode material comprises the following steps:
(1) dispersing 50g of nano wood fiber (prepared from cellulose powder by an acid hydrolysis-high pressure homogenization method) in ultrapure water (the mass concentration of the nano wood fiber is controlled to be 0.8 wt.%), carrying out vacuum filtration, naturally drying, and removing a filter membrane to obtain a transparent nano wood fiber film;
(2) soaking the nano wood fiber film obtained in the step (1) in 5mol/L nickel chloride hexahydrate solution, taking out and naturally drying, and controlling the nickel salt loading to be 48% of the total mass of the nano wood fiber film. Then carrying out high-temperature carbonization treatment in a tubular furnace to obtain a nickel/carbon nanofiber film material; wherein the carbonization temperature is controlled to be 1000 ℃, the heating rate is 5 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection;
(3) placing the nickel/carbon nanofiber membrane material obtained in the step (2) in a three-electrode electrolytic cell for potentiostatic treatment, and then cleaning with ethanol and ultrapure water to obtain a nickel/nickel oxide-loaded carbon nanofiber electrode material; wherein the electrolyte in the electrolytic cell adopts 6mol/L potassium hydroxide, the control voltage is 1V, the sensitivity is set to be 1.0e-1The treatment time was 350 s.
The electrode material prepared in this example has a low resistance of 1 Ω and a specific capacitance of 110F/g.
Example 10:
as shown in fig. 1, a method for preparing a nickel/nickel oxide-loaded carbon nanofiber electrode material comprises the following steps:
(1) dispersing 50g of nano wood fiber (prepared from cellulose powder by an acid hydrolysis-high pressure homogenization method) in ultrapure water (the mass concentration of the nano wood fiber is controlled to be 0.5 wt.%), carrying out vacuum filtration, naturally drying, and removing a filter membrane to obtain a transparent nano wood fiber film;
(2) and (2) soaking the nano wood fiber film obtained in the step (1) in a nickel nitrate hexahydrate solution of 3mol/L, taking out and naturally drying, and controlling the nickel salt loading to be 50% of the total mass of the nano wood fiber film. Then carrying out high-temperature carbonization treatment in a tubular furnace to obtain a nickel/carbon nanofiber film material; wherein the carbonization temperature is controlled to be 700 ℃, the heating rate is 5 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection;
(3) placing the nickel/carbon nanofiber membrane material obtained in the step (2) in a three-electrode electrolytic cell for potentiostatic treatment, and then cleaning with ethanol and ultrapure water to obtain a nickel/nickel oxide-loaded carbon nanofiber electrode material; wherein the electrolyte in the electrolytic cell adopts 6mol/L potassium hydroxide, the control voltage is 0.8V, the sensitivity is set to be 1.0e-1The treatment time was 500 s.
The electrode material prepared in this example had a low resistance of 1 Ω and a specific capacitance of 115F/g.
Comparative example 1:
as shown in fig. 1, a method for preparing a nickel/nickel oxide-loaded carbon nanofiber electrode material comprises the following steps:
(1) drying 50g of nano wood fiber (ultrapure water is used as a solvent) (the mass concentration of the nano wood fiber is controlled to be 0.5 wt.%), carbonizing the dried nano wood fiber in a tubular furnace at a high temperature to form the carbon nano wood fiber, wherein the carbonization temperature is controlled to be 700 ℃, the heating rate is 5 ℃/min, preserving the temperature for 2h, and introducing nitrogen for protection;
(2) and (2) uniformly mixing the carbon nano wood fiber obtained in the step (1) with nickel nitrate, and controlling the loading amount of nickel salt to be 30% of the total mass. Then carrying out high-temperature carbonization treatment in a tubular furnace to obtain a nickel/carbon nanofiber material; wherein the carbonization temperature is controlled to be 800 ℃, the heating rate is 5 ℃/min, the temperature is kept for 2h, and nitrogen is introduced for protection;
(3) placing the nickel/carbon nanofiber material obtained in the step (2) in a three-electrode electrolytic cell for potentiostatic treatment, and then cleaning with ethanol and ultrapure water to obtain a nickel/nickel oxide loaded carbon nanofiber electrode material; wherein the electrolyte in the electrolytic cell adopts 6mol/L potassium hydroxide, the control voltage is 1V, the sensitivity is set to be 1.0e-1The treatment time was 100 s.
The main difference of the comparative example from the above-mentioned embodiment is that the electrode material cannot directly support nickel on carbon fiber, and at the same time, it is difficult to form a whole electrode, and other substances such as other binders need to be added, which greatly affects the conduction of ions and electrons, thereby affecting the electrochemical performance.
Comparative example 2:
this comparative example is different from example 1 in that the mass concentration of the nano wood fiber solution was controlled to 1.0 wt.% when the nano wood fibers were dispersed in ultrapure water.
The electrode of this comparative example was measured to have a resistance value of 2.7. omega. and a specific capacitance of 110F/g.

Claims (4)

1. A preparation method of a nickel/nickel oxide-loaded carbon nanofiber electrode material is characterized by comprising the following steps:
(1) dispersing the nano wood fiber in ultrapure water, carrying out vacuum filtration, and drying to obtain a nano wood fiber film; controlling the mass concentration of the nano wood fiber solution to be 0.5-0.8wt.% when the nano wood fiber is dispersed in the ultrapure water;
(2) soaking the nano wood fiber film obtained in the step (1) in a nickel salt solution, taking out and drying the nano wood fiber film, and then carrying out high-temperature carbonization treatment to obtain a nickel/carbon nano fiber film material; controlling the mass of the nickel salt loaded on the nano wood fiber film to account for 10-70% of the total mass of the nickel/carbon nano fiber film material during soaking;
(3) carrying out electro-oxidation treatment on the nickel/carbon nanofiber thin film material obtained in the step (2) to obtain a nickel/nickel oxide loaded carbon nanofiber electrode material;
the electro-oxidation treatment comprises placing the nickel/carbon nanofiber membrane material in a three-electrode system, and treating by a potentiostatic method, wherein the electrolyte is potassium hydroxide solution, the control voltage is 0.8-1.2V, and the sensitivity is set to 1.0e-1The treatment time is 30-600 s.
2. The method according to claim 1, wherein the nano-sized wood fiber is prepared from cellulose powder by acid hydrolysis-high pressure homogenization; the nickel salt in the nickel salt solution is at least one of nickel chloride hexahydrate, nickel sulfate hexahydrate or nickel nitrate hexahydrate.
3. The preparation method according to claim 1, wherein the mass of the nickel salt loaded on the nano wood fiber film is controlled to be 30-60% of the total mass of the nickel/carbon nano fiber film material during soaking in the step (2).
4. The preparation method according to claim 1 or 2, wherein the high temperature carbonization treatment is performed in a tubular furnace under the protection of nitrogen, and the carbonization temperature is maintained at 450-.
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