CN109801792B - Preparation method and application of carbon-coated iron oxide electrode material - Google Patents
Preparation method and application of carbon-coated iron oxide electrode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon-coated iron oxide electrode material, which comprises a porous carbonaceous three-dimensional network structure matrix, wherein the carbonaceous three-dimensional network structure matrix is coated with iron oxide FeOxThe method comprises the following steps: (1) mixing the nano-cellulose solution with ferric nitrate, and stirring and dissolving to obtain a nano-cellulose/ferric nitrate mixed suspension; (2) freezing and vacuum drying the mixed suspension of the nano-cellulose and the ferric nitrate to obtain nano-cellulose/ferric nitrate aerogel; (3) and carbonizing the nano-cellulose/ferric nitrate aerogel under the protection of nitrogen to obtain the carbon-coated iron oxide electrode material. The electrode material of the invention takes a porous carbonaceous three-dimensional network structure as a matrix, so that the nano iron oxide can be well attached to the matrix and is coated by the carbon layer, and the nano iron oxide is not agglomerated, crushed and dropped due to volume change, and the product has stable electrochemical performance and high specific capacitance.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a preparation method and application of an electrode material.
Background
A supercapacitor is a new type of energy storage device between a conventional capacitor and a rechargeable battery, and its capacity can reach several hundreds to thousands of methods. Compared with the traditional capacitor, the capacitor has larger capacity, specific energy or capacity density, wider working temperature range and extremely long service life; compared with a storage battery, the novel energy-saving battery has higher specific power, can release extra-large current instantly, and has the characteristics of short charging time, high charging efficiency, long cycle service life, no memory effect, no pollution to the environment, no maintenance and the like. Electrochemical capacitors can be divided into two categories according to their energy storage mechanism: one is an electric double layer capacitor based on the principle of an electric double layer of an interface between a high specific surface carbon material and a solution; another class is faraday photonics capacitors based on underpotential deposition or redox processes of two-dimensional or quasi-two-dimensional material surfaces. With the rapid development of intelligent electronic devices such as portable devices and wearable devices, the application of energy storage devices such as super capacitors and metal ion batteries is further promoted, and the core of the energy storage devices is the preparation of electrode materials of the energy storage devices, so that the finding of an electrode material which is low in cost, stable in electrochemical performance and free of pollution has very important significance.
The transition metal oxide has high theoretical specific capacitance and good conductivity, and is widely applied to electrode materials of Faraday pseudocapacitors and lithium batteries. However, the low conductivity and large volume effect during the circulation process often result in agglomeration and pulverization of the active material, resulting in low electrochemical performance and short cycle life. The carbon-coated transition metal oxide has good electrochemical stability and low cost as a supercapacitor electrode material, and is a hot point of research all the time, particularly a carbon-based transition metal composite material with a 3D structure is concerned due to the unique structure of the carbon-coated transition metal oxide. Currently, various types of carbon-based transition metal oxides are prepared, such as compounding with graphene, carbon nanotubes and other materials, but the preparation process is complicated and the cost is high, so that commercialization is difficult to realize. Therefore, the development of the supercapacitor electrode material of the carbon-coated transition metal oxide, which has the advantages of simple synthesis method, low cost, good electrochemical performance and industrial application prospect, has obvious practical significance.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background art, and provide a preparation method and application of a carbon-coated iron oxide electrode material which is simple in synthesis method, low in cost, good in electrochemical performance and has a 3D network structure. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
preparation of carbon-coated iron oxide electrode materialThe method comprises the step of preparing a porous carbonaceous three-dimensional network structure matrix, wherein the carbonaceous three-dimensional network structure matrix is coated with iron oxide FeOx(mixture of Fe and iron oxides) comprising the steps of:
(1) mixing the nano-cellulose solution with ferric nitrate, and stirring and dissolving to obtain a nano-cellulose/ferric nitrate mixed suspension;
(2) freezing and vacuum-drying the mixed nano-cellulose/ferric nitrate suspension obtained in the step (1) to obtain nano-cellulose/ferric nitrate aerogel;
(3) and (3) carbonizing the nano-cellulose/ferric nitrate aerogel obtained in the step (2) under the protection of nitrogen to obtain the carbon-coated iron oxide electrode material.
In the preparation method, preferably, the pore diameter of the carbonaceous three-dimensional network structure matrix is 0.005-3 μm, the proportion of mesopores is not less than 50%, and the density of the electrode material is 2.65-3.8 g/m2. The carbon-coated iron oxide electrode material has a porous structure and more mesopores, and compared with micropores and macropores, the active substance can be better adsorbed on the mesopores.
In the above preparation method, preferably, in the step (1), the solid content of the nanocellulose solution is 0.2 to 1.0% (more preferably, 0.5%), and the preparation method of the nanocellulose solution includes the following steps: mixing lignocellulose powder according to a solid-liquid ratio of 1: 20, adding the mixture into concentrated sulfuric acid with the mass fraction of 40-60%, stirring the mixture in a water bath for 1-3 hours at the temperature of 35-60 ℃ until cellulose is hydrolyzed, then washing the mixture with ultrapure water to adjust the pH value to 6-7, and then carrying out high-pressure homogenization treatment for 15-25 cycles to obtain the uniformly dispersed nano cellulose solution. The aerogel obtained from the nano-cellulose solution with the solid content has a good form, the porosity of the electrode material obtained after carbonization is large and can reach 94% at most, and the electrochemical performance is excellent.
In the above preparation method, preferably, in the step (1), the mass ratio of the carbon content to the iron content in the nanocellulose/ferric nitrate mixed suspension is controlled to be (1: 5): (5:1). The mass ratio of the carbon content to the iron content has a greater influence on the morphological change of the aerogel, so that the electrochemical performance of the electrode material is improved if the mass ratio of the carbon content to the iron content is less than 1: 5, a large part of ferric nitrate cannot be loaded on the nano-cellulose, and the ferric nitrate has poor uniform dispersibility in the nano-cellulose; if the dosage ratio is higher than 5:1, only a small amount of ferric nitrate is loaded on the nano-cellulose, and finally the obtained electrode material has poor conductivity. In view of the above-mentioned influence of the mass ratio of the carbon content to the iron content, it is more preferable to control the mass ratio of the carbon content to the iron content in the nanocellulose/iron nitrate mixed suspension to be 2: 1, the electrochemical performance of the electrode material is optimal.
In the preparation method, preferably, the stirring speed is controlled to be 150-600 rpm and the stirring time is controlled to be 30-40 min during stirring and dissolving.
In the preparation method, preferably, during the freezing treatment, the freezing temperature is controlled to be-60 to-40 ℃, and the freezing time is 10 to 12 hours; during vacuum drying treatment, the mixture is firstly dried in vacuum at-60 to-40 ℃ for 6 to 9 hours and then dried in vacuum at 10 to 30 ℃ for 15 to 20 hours.
In the preparation method, preferably, the carbonization treatment is carried out in an atmosphere tube furnace, the carbonization temperature is controlled to be 700-900 ℃, the carbonization time is 1-3 h, and the flow rate of nitrogen is controlled to be 100-200 mL/min. The carbonization temperature has great influence on the performance of the final product, and the nanocellulose can be thermally decomposed into a carbon material within 700-900 ℃ and can coat FeOxFe/Fe produced by thermal reduction3O4The porous active substance carrier material with good conductivity, excellent loading effect and certain mechanical property is obtained. If it is lower than the above temperature, the resulting support material cannot be completely carbonized to cause deterioration in conductivity. If the temperature is higher than the above range, the carbon material cannot be coated with Fe/Fe3O4And a large amount of elemental iron is generated, so that the electrochemical stability of the electrode material is reduced.
As a general technical concept, the invention also provides an application of the carbon-coated iron oxide electrode material obtained by the preparation method, the carbon-coated iron oxide electrode material is used for preparing an electrode plate of a super capacitor, and the preparation method of the electrode plate of the super capacitor comprises the following steps:
(1) grinding the carbon-coated iron oxide electrode material into powder, and mixing with acetylene black according to the weight ratio of 8: 1, adding an ethanol solution, and grinding into slurry for 30-40 min;
(2) PVDF (polyvinylidene fluoride) with the mass being 8 times that of the carbon-coated iron oxide electrode material is stirred and dissolved by NMP (N-methyl pyrrolidone), added into the slurry obtained in the step (1), stirred to obtain an active substance of the electrode material of the supercapacitor, and stirred at the speed of 200-500 rpm for 1-3 hours;
(3) and (3) uniformly coating the active substance of the electrode material of the super capacitor obtained in the step (2) on the treated foam nickel sheet to obtain the electrode sheet of the super capacitor.
The nano-cellulose is a natural, reproducible and most abundant high-molecular polymer, has excellent biocompatibility and degradability, high specific surface area and good dispersibility, and has a plurality of electrochemical reaction active sites. The nano iron oxide is an important inorganic material, has high abundance in the nature, low price, no toxicity and environmental friendliness, is a potential candidate electrode material for developing an electrochemical capacitor electrode, and has large theoretical specific capacity. After mixing the nano-cellulose and the ferric nitrate solution, iron ions with excellent conductivity can be well dispersed and attached to the nano-cellulose by stirring. Freezing the obtained suspension to form a stable network skeleton structure of the ferric nitrate coated by the nano-cellulose, and then discharging the ice crystals in the suspension in a sublimation manner to form the aerogel through vacuum drying. And (2) carrying out pyrolysis on the nano-cellulose/ferric nitrate aerogel in an atmosphere tubular furnace under the protection of nitrogen gas, so that the iron/ferroferric oxide obtained by high-temperature conversion of the carbon layer pyrolysis coating forms a stable 3D network structure, and thus the porous carbon-coated metal oxide electrode active substance with high specific capacitance and stable electrochemical performance is obtained.
Compared with the prior art, the invention has the advantages that:
1. the carbon-coated iron oxide electrode material takes a porous carbonaceous three-dimensional network structure as a matrix, the matrix provides a large number of mesopores, so that the nano iron oxide can be well attached to the matrix, and the nano iron oxide is coated by the carbon layer, so that the nano iron oxide is not agglomerated, crushed and dropped due to volume change, and the product has stable electrochemical performance and high specific capacitance. Through cycle life test, the specific capacitance of the capacitor after 2000 circles of constant current charge and discharge is kept to be 91.4 percent of the initial value, and when the current density is 0.5A/g, the specific capacitance can be as high as 57.7F/g.
2. The method has the advantages of simple operation method, strong controllability, wide source of raw material plant cellulose and low production cost, and meets the strategic goal of green sustainable development.
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 an SEM image of the carbon-coated iron oxide electrode material prepared in example 1.
Fig. 2 is a physical diagram of the nano-cellulose/ferric nitrate aerogel prepared in example 1.
Fig. 3 is a schematic view of the electrode sheet prepared in example 1.
Fig. 4 is a cyclic voltammogram of the electrode sheet prepared in example 1.
Fig. 5 is a constant current charge and discharge curve of the electrode sheet prepared in example 1.
Fig. 6 is a cyclic voltammogram of the electrode sheet prepared in example 2.
Fig. 7 is a constant current charge and discharge curve of the electrode sheet prepared in example 2.
Fig. 8 is a cyclic voltammogram of the electrode sheet prepared in example 3.
Fig. 9 is a constant current charge and discharge curve of the electrode sheet prepared in example 3.
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:
a carbon-coated iron oxide electrode material comprises a porous carbonaceous three-dimensional network structure matrix, wherein the carbonaceous three-dimensional network structure matrix is coated with iron oxide FeOx. The pore diameter of the carbonaceous three-dimensional network structure matrix is about 0.005-3 mu m, the proportion of mesopores is not less than 50 percent, and the density of the electrode material is about 2.65-3.8 g/m2. The preparation method of the carbon-coated iron oxide electrode material comprises the following steps:
(1) preparing a nano-cellulose solution: mixing lignocellulose powder according to a solid-liquid ratio of 1: 20, adding the mixture into concentrated sulfuric acid with the mass fraction of 48%, stirring the mixture in water bath for 2 hours at 45 ℃ until the cellulose finishes the hydrolysis process, then washing the mixture with ultrapure water to adjust the pH value to 6-7, and then carrying out high-pressure homogenization treatment for 15-25 cycles to obtain a uniformly dispersed nano cellulose solution;
(2) mixing a nano-cellulose solution with a solid content of 0.5% with ferric nitrate nonahydrate, stirring on a magnetic stirrer at a stirring speed of 600rpm for 40min to obtain a nano-cellulose/ferric nitrate mixed suspension, and controlling the mass ratio of the carbon content to the iron content in the suspension to be 5: 1;
(3) injecting the mixed suspension of the nano-cellulose and the ferric nitrate in the step (2) into a mould, placing the mould in a freeze dryer for freezing at the freezing temperature of-50 ℃ for 12 hours, carrying out vacuum drying at the temperature of-50 ℃ for 6 hours, then carrying out vacuum drying at the temperature of 20 ℃ for 15 hours, and demoulding to obtain the nano-cellulose/ferric nitrate aerogel;
(4) and (4) carrying out pyrolysis treatment on the nano-cellulose/ferric nitrate aerogel obtained in the step (3) in an atmosphere tube furnace at 800 ℃ under the protection of nitrogen, keeping the temperature for 2 hours at the flow rate of 100mL/min of nitrogen, and obtaining the carbon-coated iron oxide electrode material with the 3D network structure after carbonization.
The SEM image of the carbon-coated iron oxide electrode material prepared in this example is shown in fig. 1, and it can be seen that the iron oxide FeO is coated in the carbonaceous three-dimensional network matrixxAnd a network structure with cross-connections is formed.
The method for preparing the electrode plate of the supercapacitor by using the carbon-coated iron oxide comprises the following steps:
(1) the carbon-coated iron oxide electrode material is put in an agate mortar and ground into powder, and the powder is mixed with acetylene black 8: 1, and grinding into slurry by dropping a few drops of ethanol solution for 30 min;
(2) placing the slurry in a weighing bottle, taking PVDF (polyvinylidene fluoride) with 8 times of mass of the carbon-coated iron oxide electrode material, dissolving the PVDF with NMP (N-methyl pyrrolidone), adding the dissolved PVDF into the weighing bottle, placing the weighing bottle on a magnetic stirrer, and stirring at a stirring speed of 500rpm for 3 hours to obtain an active substance of the electrode material of the supercapacitor;
(3) and (3) uniformly coating the active substance of the electrode material of the super capacitor on the treated foam nickel sheet, wherein the coating area is 1cm multiplied by 1cm, and thus obtaining the electrode sheet of the super capacitor.
As shown in fig. 2, it can be seen from fig. 2 that the nanocellulose/ferric nitrate aerogel prepared in this example has a good appearance, morphology and structure of the carbon-coated iron oxide electrode material prepared in this example.
As shown in fig. 3, it can be seen from fig. 3 that the electrode sheet of the supercapacitor prepared in this embodiment has the active material uniformly coated on the surface of the nickel foam, so that the accuracy of the electrochemical test is ensured.
Fig. 4 and 5 show cyclic voltammetry curves and constant current charge and discharge curves of the electrode sheet of the supercapacitor prepared in this example, and it can be seen from the graphs that the specific capacitance is 27.8F/g when the current density is 0.5A/g. Through cycle life test, the specific capacitance of the capacitor is kept to be 89.1 percent of the initial value after 2000 circles of constant current charging and discharging.
Example 2:
a carbon-coated iron oxide electrode material comprises a porous carbonaceous three-dimensional network structure matrix, wherein the carbonaceous three-dimensional network structure matrix is coated with iron oxide FeOx. The pore diameter of the carbonaceous three-dimensional network structure matrix is about 0.005-3 mu m, the proportion of mesopores is not less than 50 percent, and the density of the electrode material is about 2.65-3.8 g/m2. The preparation method of the carbon-coated iron oxide electrode material comprises the following steps:
(1) preparing a nano-cellulose solution: mixing lignocellulose powder according to a solid-liquid ratio of 1: 20, adding the mixture into concentrated sulfuric acid with the mass fraction of 48%, stirring the mixture in a water bath for 2 hours at 48 ℃ until the cellulose is hydrolyzed, washing the mixture with ultrapure water to adjust the pH value to 6-7, and performing high-pressure homogenization treatment for 15-25 cycles to obtain a uniformly dispersed nano-cellulose solution;
(2) mixing a nano-cellulose solution with a solid content of 0.5% with ferric nitrate nonahydrate, stirring on a magnetic stirrer at a stirring speed of 600rpm for 40min to obtain a nano-cellulose/ferric nitrate mixed suspension, and controlling the mass ratio of the carbon content to the iron content in the suspension to be 2: 1;
(3) injecting the mixed suspension of the nano-cellulose and the ferric nitrate in the step (2) into a mould, placing the mould in a freeze dryer for freezing at the freezing temperature of-50 ℃ for 12 hours, carrying out vacuum drying at the temperature of-50 ℃ for 6 hours, then carrying out vacuum drying at the temperature of 20 ℃ for 15 hours, and demoulding to obtain the nano-cellulose/ferric nitrate aerogel;
(4) and (4) carrying out pyrolysis treatment on the nano-cellulose/ferric nitrate aerogel obtained in the step (3) in an atmosphere tubular furnace at 825 ℃ under the protection of nitrogen, wherein the heat preservation time is 1.2h, the flow rate of the nitrogen is 100mL/min, and after carbonization, obtaining the carbon-coated iron oxide electrode material with the 3D network structure.
The method for preparing the electrode plate of the supercapacitor by using the carbon-coated iron oxide comprises the following steps:
(1) the carbon-coated iron oxide electrode material is put in an agate mortar and ground into powder, and the powder is mixed with acetylene black 8: 1, and grinding into slurry by dropping a few drops of ethanol solution for 30 min;
(2) placing the slurry in a weighing bottle, taking PVDF (polyvinylidene fluoride) with 8 times of mass of the carbon-coated iron oxide electrode material, dissolving the PVDF with NMP (N-methyl pyrrolidone), adding the dissolved PVDF into the weighing bottle, placing the weighing bottle on a magnetic stirrer, and stirring at a stirring speed of 500rpm for 3 hours to obtain an active substance of the electrode material of the supercapacitor;
(3) and (3) uniformly coating the active substance of the electrode material of the super capacitor on the treated foam nickel sheet, wherein the coating area is 1cm multiplied by 1cm, and thus obtaining the electrode sheet of the super capacitor.
The cyclic voltammetry curve and the constant current charge and discharge curve of the electrode sheet of the supercapacitor prepared in this example are shown in fig. 6 and 7, respectively, and it is understood from the graphs that the specific capacitance is 57.7F/g when the current density is 0.5A/g. Through cycle life test, the specific capacitance of the capacitor is maintained to be 91.4% of the initial value after 2000 circles of constant current charging and discharging.
Example 3:
a carbon-coated iron oxide electrode material comprises a porous carbonaceous three-dimensional network structure matrix, wherein the carbonaceous three-dimensional network structure matrix is coated with iron oxide FeOx. The pore diameter of the carbonaceous three-dimensional network structure matrix is about 0.005-3 mu m, the proportion of mesopores is not less than 50 percent, and the density of the electrode material is about 2.65-3.8 g/m2. The preparation method of the carbon-coated iron oxide electrode material comprises the following steps:
(1) preparing a nano-cellulose solution: mixing lignocellulose powder according to a solid-liquid ratio of 1: 20, adding the mixture into concentrated sulfuric acid with the mass fraction of 48%, stirring the mixture in water bath for 2 hours at 45 ℃ until the cellulose finishes the hydrolysis process, then washing the mixture with ultrapure water to adjust the pH value to 6-7, and then carrying out high-pressure homogenization treatment for 15-25 cycles to obtain a uniformly dispersed nano cellulose solution;
(2) mixing a nano-cellulose solution with a solid content of 0.5% with ferric nitrate nonahydrate, stirring on a magnetic stirrer at a stirring speed of 600rpm for 40min to obtain a nano-cellulose/ferric nitrate mixed suspension, and controlling the mass ratio of the carbon content to the iron content in the suspension to be 1: 1;
(3) injecting the mixed suspension of the nano-cellulose and the ferric nitrate in the step (2) into a mould, placing the mould in a freeze dryer for freezing at the freezing temperature of-50 ℃ for 12 hours, carrying out vacuum drying at the temperature of-50 ℃ for 6 hours, then carrying out vacuum drying at the temperature of 20 ℃ for 15 hours, and demoulding to obtain the nano-cellulose/ferric nitrate aerogel;
(4) and (4) carrying out pyrolysis treatment on the nano-cellulose/ferric nitrate aerogel obtained in the step (3) in an atmosphere tubular furnace at 800 ℃ under the protection of nitrogen, keeping the temperature for 2 hours, and obtaining the carbon-coated iron oxide electrode material with the 3D network structure after carbonization, wherein the flow rate of the nitrogen is 100 mL/min.
The method for preparing the electrode plate of the supercapacitor by using the carbon-coated iron oxide comprises the following steps:
(1) the carbon-coated iron oxide electrode material is put in an agate mortar and ground into powder, and the powder is mixed with acetylene black 8: 1, and grinding into slurry by dropping a few drops of ethanol solution for 30 min;
(2) placing the slurry in a weighing bottle, taking PVDF (polyvinylidene fluoride) with 8 times of mass of the carbon-coated iron oxide electrode material, dissolving the PVDF with NMP (N-methyl pyrrolidone), adding the dissolved PVDF into the weighing bottle, placing the weighing bottle on a magnetic stirrer, and stirring at a stirring speed of 500rpm for 3 hours to obtain an active substance of the electrode material of the supercapacitor;
(3) and (3) uniformly coating the active substance of the electrode material of the super capacitor on the treated foam nickel sheet, wherein the coating area is 1cm multiplied by 1cm, and thus obtaining the electrode sheet of the super capacitor.
Fig. 8 and 9 show cyclic voltammetry curves and constant current charge and discharge curves of the electrode sheet of the supercapacitor prepared in this example, and it is understood from the graphs that the specific capacitance is 37.2.F/g when the current density is 0.5A/g. Through cycle life test, the specific capacitance is kept to be 90.6% of the initial value after 2000 circles of constant current charging and discharging.
Claims (6)
1. Carbon-coated iron oxide electrode materialThe preparation method of the material is characterized in that the electrode material comprises a porous carbonaceous three-dimensional network structure matrix, and the carbonaceous three-dimensional network structure matrix is coated with ferric oxide FeOxThe method comprises the following steps:
(1) mixing the nano-cellulose solution with ferric nitrate, and stirring and dissolving to obtain a nano-cellulose/ferric nitrate mixed suspension;
(2) freezing and vacuum-drying the mixed nano-cellulose/ferric nitrate suspension obtained in the step (1) to obtain nano-cellulose/ferric nitrate aerogel;
(3) carbonizing the nano-cellulose/ferric nitrate aerogel obtained in the step (2) under the protection of nitrogen to obtain a carbon-coated iron oxide electrode material;
the pore diameter of the carbonaceous three-dimensional network structure matrix is 0.005-3 mu m, the proportion of mesopores is not less than 50%, and the density of the electrode material is 2.65-3.8 g/m2；
In the step (1), the solid content of the nano-cellulose solution is 0.2-1.0%, and the preparation method of the nano-cellulose solution comprises the following steps: mixing lignocellulose powder according to a solid-liquid ratio of 1: 20, adding the mixture into concentrated sulfuric acid with the mass fraction of 40-60%, stirring the mixture in a water bath for 1-3 hours at the temperature of 35-60 ℃ until cellulose is hydrolyzed, washing the mixture with ultrapure water to adjust the pH value to 6-7, and performing high-pressure homogenization treatment for 15-25 cycles to obtain a uniformly dispersed nano cellulose solution;
in the step (1), the mass ratio of the carbon content to the iron content in the mixed nano-cellulose/ferric nitrate suspension is controlled to be (1: 5): (5:1).
2. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the carbon content to the iron content in the nanocellulose/ferric nitrate mixed suspension is controlled to be 2: 1.
3. the method according to claim 1 or 2, wherein the stirring speed is controlled to be 150 to 600rpm and the stirring time is controlled to be 30 to 40min during the stirring and dissolving.
4. The preparation method according to claim 1 or 2, wherein the freezing temperature is controlled to be-60 to-40 ℃ and the freezing time is controlled to be 10 to 12 hours during the freezing treatment; and during vacuum drying treatment, firstly, vacuum drying at-60 to-40 ℃ for 6-9 h, and then vacuum drying at 10-30 ℃ for 15-20 h.
5. The method according to claim 1 or 2, wherein the carbonization treatment is performed in an atmosphere tube furnace, the carbonization temperature is controlled to 700 to 900 ℃, the carbonization time is controlled to 1 to 3 hours, and the flow rate of nitrogen gas is controlled to 100 to 200 mL/min.
6. The application of the carbon-coated iron oxide electrode material obtained by the preparation method according to any one of claims 1 to 5, wherein the carbon-coated iron oxide electrode material is used for preparing an electrode plate of a super capacitor, and the preparation method of the electrode plate of the super capacitor comprises the following steps:
(1) grinding the carbon-coated iron oxide electrode material into powder, and mixing with acetylene black according to the weight ratio of 8: 1, adding an ethanol solution, and grinding into slurry for 30-40 min;
(2) PVDF (polyvinylidene fluoride) with the mass being 8 times that of the carbon-coated iron oxide electrode material is stirred and dissolved by NMP (N-methyl pyrrolidone), added into the slurry obtained in the step (1), stirred to obtain an active substance of the electrode material of the supercapacitor, and stirred at the speed of 200-500 rpm for 1-3 hours;
(3) and (3) uniformly coating the active substance of the electrode material of the super capacitor obtained in the step (2) on the treated foam nickel sheet to obtain the electrode sheet of the super capacitor.
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| CN104752069A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method of metallic oxide or metallic oxide composite material |
| CN107134373A (en) * | 2017-04-25 | 2017-09-05 | 武汉大学 | A kind of carbon aerogels/metal oxide composite and preparation method and application |
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