CN111048323B - Metal oxide electrode based on carbon material and preparation method thereof - Google Patents
Metal oxide electrode based on carbon material and preparation method thereof Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention discloses a metal oxide electrode based on carbon material, which comprises NiCo prepared by hydrothermal synthesis method2O4/GO composite material and NiFe prepared by hydrothermal synthesis method2O4a/CNTsCOOH composite material, and combining the two composite materials; the combination mode is made of NiFe2O4Insertion of/CNTsCOOH composite into NiCo2O4A three-dimensional mesoporous structure is formed between the GO sheets; and preparation of NiCo2O4Method for preparing/GO composite material and NiFe2O4A method for preparing/CNTsCOOH composite material. The electrode prepared by the preparation method introduces a high-conductivity carbon material to form a hybrid composite material with the high-conductivity carbon material, so that the conductivity and the structural stability of the material are enhanced, the multiplying power performance and the cycle life of the super capacitor are improved, the overall function is complete, and the practicability is high.
Description
Technical Field
The invention relates to the technical field of electrode manufacturing, in particular to a metal oxide electrode based on a carbon material and a preparation method thereof.
Background
A super capacitor is a novel device for storing energy, has a high power density, and is widely used in energy storage devices, power supply devices, and many electronic devices due to its advantages of short charging time, long cycle life, and environmental friendliness. According to the difference of energy storage mechanism, the super capacitor is divided into two categories: one type is Electric Double Layer Capacitors (EDLCs) which store electrical energy in the form of static electricity by forming a Helmholtz layer between an electrode and an electrolyte, using a carbon material as an electrode material; another type is a faraday capacitor, also known as a pseudocapacitor or pseudocapacitor, which stores electrical energy electrochemically by redox reactions using metal oxides and conducting polymers as electrode materials. Different from a relatively traditional chemical power supply, the super capacitor is a power supply between a traditional capacitor and a battery, has excellent pulse charge and discharge performance, has higher power density than a storage battery, and has higher energy density than a traditional capacitor.
Supercapacitors typically comprise four components, a bipolar electrode, an electrolyte, a current collector, and a separator, wherein the structure and performance of the electrode material are critical factors in determining certain major performance parameters of the capacitor. As an electrode material of a super capacitor, the material is required to have high specific capacity and low internal resistance so as to meet the requirements of high current and rapid charge and discharge of the super capacitor. Meanwhile, the electrode material is required to be capable of easily forming an electric double layer capacitance or a faraday pseudo-capacitance at the interface between the electrode and the electrolyte, and to have appropriate chemical stability, mechanical stability, and good conductivity to electrons and ions for itself. Commonly used electrode materials are carbon-based material electrodes, metal oxide electrodes and conductive polymer electrodes.
(1) Carbon electrode
The carbon material has very stable chemical properties, good corrosion resistance and excellent electric and heat conduction capacity, and is the most widely applied electrode material in the carbon material. The excellent carbon electrode material of the super capacitor needs to consider the mass specific capacity and the volume specific capacity while planning the performances of aperture dispersion, apparent density, conductivity and the like so as to greatly improve the comprehensive performance of the capacitor. Besides generating Helmholtz layer, the surface of the material can generate pseudocapacitance reaction. At present, carbon nanotubes and graphene are representative of widely studied supercapacitor carbon electrode materials.
Carbon Nanotubes (CNTs) are hollow round tubes made of hexagonally arranged carbon atoms, have a large specific surface area, and are one-dimensional quantum materials with special structures. In addition, the carbon nanotube has sp hybridized C, three hybridized bonds are connected to form ring to form six-membered ring, and the rest hybridized bonds can connect functional groups (such as hydroxyl, carboxyl, etc.) capable of generating pseudo capacitance reaction. Therefore, the carbon nano tube not only can form an electric double layer capacitor, but also can fully utilize the pseudocapacitance energy storage principle. Wherein, the multi-wall carbon nano tube with short tube length, small tube diameter and lower graphitization degree is more suitable to be used as an electrode material of a double electric layer capacitor. Research work for using carbon nanotubes as electrode materials of a super capacitor is reported earlier in the prior art, and the research work uses multi-wall carbon nanotubes to prepare a film electrode, the specific capacitance of the film electrode can reach 49-113F/g in a sulfuric acid aqueous solution, and the power density of the film electrode exceeds 8 kW/kg. At present, carbon nanotubes cannot be industrially produced, and the related art is not mature, so that the price is very high. In addition, its use in supercapacitors is also under investigation, at a longer distance from commercial production.
Graphene (Graphene), which is a single-layer graphite sheet composed of carbon atoms, is one of the thinnest materials known and is very strong and stable; as a simple substance, it transports electrons at room temperature faster than any known conductor. The graphene has a very wide application prospect in high-performance ultrathin high-power-consumption electronic products such as smart phones, tablet computers, ultrathin LCD televisions and the like. The existing research group prepares chemically modified graphene by using a hydrazine hydrate reduction method, and carries out preliminary research on the capacitance performance of the chemically modified graphene, and the research shows that the conductivity of the graphene reaches 2 multiplied by 102S/m, the specific surface area also reaches 705m2/g, the specific capacitance in aqueous electrolyte and inorganic electrolyte is 135F/g and 99F/g respectively, and the graphene has higher rate characteristic.
(2) Metal oxide electrode
The metal oxide stores energy by utilizing the fact that redox reaction of electrode active substances rapidly occurs on the surface and the near surface of an electrode, and the faradaic pseudo capacitance generated in the super capacitor is 10-100 times of the electric double layer capacitance of the surface of a carbon-based electrode material. In the current metal oxide electrode capacitor, the research on a ruthenium dioxide (RuO2) and sulfuric acid aqueous solution system is the forefront, and the specific capacitance can reach 760F/g. However, Ru is a rare metal, and its commercial use is hindered due to its expensive price. Therefore, the research has been gradually conducted to inexpensive transition metal oxides of Mn, Ni, Co, and the like. Among them, increasing the electrochemical activity of an electrode active material and increasing the active surface area are effective ways to increase the specific capacitance thereof.
(3) Conductive polymer electrode
As a novel electrode material, the conductive polymer can form a corresponding polymer structure through molecular design, and has the advantages of low cost, high capacity, short charging and discharging time and environmental friendliness, so that the conductive polymer becomes a new hotspot for researching electrode materials of the super capacitor. The conjugated structure of the polymer electrode improves the delocalization of electrons, can generally obtain higher working potential which is more than 3 times of that of a carbon material, and has higher research value. Currently, the main studied conductive polymers include polyaniline, polythiophene, polypyrrole, and their derivatives. It has a major problem that the cycle performance is not stable enough, and the volume change occurs during the long-term charge and discharge, resulting in the degradation of the performance. In order to improve the cycling stability of the conductive polymer electrode, a conductive polymer having excellent doping properties is developed or compounded with other electrode materials.
Wherein MnO is used2Electrode of/graphene composite material, MnO thereof2The preparation method is simple, the electrochemical performance is outstanding due to the structural characteristics of proper crystal form, porosity and the like, but the application of the electrochemical performance in the super capacitor is limited due to the lower conductivity and the lower load rate, so that MnO can be used2Deposited on the surface of graphene to compensate for these defects. At present, foamed nickel is used as a template, three-dimensional porous graphene (ERGO) with a honeycomb structure on the surface is introduced, and MnO is added2The nano-wire-shaped composite is deposited on the surface of the three-dimensional graphene, and the maximum specific capacitance value of the prepared nano-wire-shaped composite reaches 476F/g in the detection of a three-electrode system.
Wherein RuO is adopted2Electrode of/graphene composite material, RuO thereof2The transition metal oxide is the earliest studied transition metal oxide, is an excellent pseudo-capacitance electrode material due to good conductivity, high capacity and small internal resistance, but is limited in application due to expensive price, so that many researches are focused on reducing the using amount of the transition metal oxide to reduce the preparation cost, and one of the main ways is to compound the transition metal oxide with graphene. RuO has been prepared by a one-step hydrothermal method2The graphene/graphene composite is subjected to electrochemical performance test in a three-electrode system. It was found that when the current density was 0.5A/g, the maximum specific capacitance value of the composite was 471F/g, and the capacitance retention after 3000 charge-discharge cycles was still 92%.
The electrode made of the NiO/graphene composite material has the advantages of high theoretical pseudo capacitance, good cycle reversibility and the like, and the electrode material of the supercapacitor with excellent electrochemical performance can be obtained by compounding the NiO/graphene composite material with the graphene. GO and Ni (NO)3)2And urea is used as a raw material, a granular NiO/graphene compound is prepared by a one-step hydrothermal method, and is subjected to electrochemical test in a three-electrode system, and the result shows that the specific capacitance of the compound reaches 429.7F/g at 0.2A/g, and the retention rate of the capacitance is still 86.1% after 2000 cycles.
Wherein, Co is used3O4Electrode of/graphene composite material, Co thereof3O4The graphene composite material has a high theoretical capacitance value (3560F/g), and also has excellent oxidation-reduction performance, but the application of the graphene composite material in a super capacitor is limited by the low rate performance and the low cycle stability, and the defects of the super capacitor composite material can be effectively overcome by compounding the graphene composite material with the graphene. At present, carbon black is used as a modifier of graphene, so that the stacking of graphene sheets is effectively inhibited, the utilization rate of the surface of the graphene is also improved, and the specific capacitance of the prepared compound is improved to 341F/g when the scanning rate is 10mV/s through a three-electrode test.
Wherein NiCo is adopted2O4The van der waals force exists between the graphene sheets of the electrode made of the graphene composite material, so that the electrode is easy to stack and agglomerate, and the specific surface area and the specific capacity are reduced. The metal oxide is introduced to be compounded with the graphene, so that the nano particles enter between the stacked graphene sheet layers, the graphene sheets can be effectively prevented from being overlapped again, and higher charge capacity can be maintained.
Compared with a single metal oxide/graphene compound, the binary metal oxide/graphene compound is characterized in that more metal ions participate in redox reaction by introducing another metal ion into one metal oxide, so that more charges are stored in an electrode, and the energy density and the power density are improved; and through the interaction of two metal ions, the electrode material has higher conductivity, and the electrochemical performance of the electrode material is greatly improved.
The nickel/cobalt electrode material has proved to have high specific capacitance, good rate capability and stability, abundant reserves and low price, and is a green electrode material with great development potential. Compared with hydroxide, the nickel/cobalt oxide has more stable structure in air and alkali liquor and excellent capacitance cycling stability. And Ni and Co are cheap and easily available, so NiCo2O4Is a super capacitor electrode material which is relatively consistent with expectations.
Mixing NiCo2O4Growing on the graphene conductive net to form the graphene/NiCo with a double-net structure2O4The conductivity of the composite material is as high as 22.6S/m and is about NiCo2O4266 times of (0.085S/m). As electrodes, graphene/NiCo2O4Has a specific capacitance of 1710.7F/g. When the current density is 20A/g, the specific capacitance is still 1467.7F/g, and after 3000 times of continuous charge and discharge cycles under the current density of 10A/g, the capacitance is only attenuated by 4.4%, which fully explains the excellent rate capability and cycle stability of the material.
In addition, the granular NiCo is successfully prepared by using a hydrothermal method by taking nickel chloride, cobalt chloride and GO as raw materials and PDDA as a reducing agent and a stabilizing agent2O4The graphene composite is used for testing the electrochemical properties of the graphene composite in a three-electrode system. The results show that the maximum specific capacitance value of the composite is 676.1F/g at a scan rate of 5 mV/S.
In summary, the metal oxide electrode materials belong to semiconductor materials, and their overall conductivity is not satisfactory. In addition, in the preparation process, the specific surface area of the material is seriously reduced due to the agglomeration phenomenon of the nano particles, and the overall effect is poor. Accordingly, the invention provides a metal oxide electrode based on a carbon material and a preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a metal oxide electrode based on a carbon material and a preparation method thereof.
In order to solve the technical problem, the invention aims to realize that: the invention relates to a metal oxide electrode based on carbon material, which comprises NiCo prepared by hydrothermal synthesis method2O4/GO composite material and NiFe prepared by hydrothermal synthesis method2O4a/CNTsCOOH composite material, and combining the two composite materials; the combination mode is made of NiFe2O4Insertion of/CNTsCOOH composite into NiCo2O4The layers of/GO form a three-dimensional mesoporous structure.
The invention relates to a metal oxide electrode based on a carbon material and a preparation method thereof, wherein the NiCo is2O4The preparation steps of the/GO composite material are as follows:
s1, preparing GO suspension: weighing 0.100g of GO by using an electronic balance, putting the GO into a 100ml beaker, adding 50ml of deionized water, and performing ultrasonic dispersion for 30min to obtain a GO suspension;
s2, adding NiCo2O4Precursor: weighing NiCo with a certain mass by using an electronic balance2O4Adding the precursor into the GO suspension liquid subjected to ultrasonic dispersion, installing a stirring paddle, and stirring for 30min by using an electric stirrer until the medicine is dissolved;
s3, carrying out hydrothermal reaction: after stirring, pouring reactants into a polytetrafluoroethylene lining, washing the reactants which are not poured out of a beaker with 10ml of deionized water, pouring the reactants into the lining, putting the reactants into a hydrothermal reaction kettle, screwing down a cover, and putting the reactants into an air-blast drying oven for constant-temperature reaction for 8 hours at 120 ℃;
s4, after the reaction is finished, taking the reaction kettle out of the air-blast drying box, and naturally cooling;
s5, suction filtration: repeatedly washing the cooled reactant with deionized water for 3 times to remove unreacted ions;
s6, after the suction filtration is finished, putting a washing product on the filter membrane into a clean and dry culture dish, wrapping an opening with an aluminum foil, pricking a proper amount of small holes on the aluminum foil to prevent pollution, putting the culture dish into a blast drying oven, and drying for 12 hours at 70 ℃;
s7, after the sample is dried, grinding the sample into powder by using an agate mortar, putting the powder into a 30ml corundum crucible, and roasting the powder for 2 hours in a muffle furnace at the temperature of below 400 ℃;
s8, after roasting is finished, taking out the crucible, cooling at room temperature, filling a roasted product in the crucible into a plastic package bag after cooling, attaching a label, and putting the product into a drying dish.
The invention is further configured to: the ultrasonic dispersion in the step S1 is that the oscillation time interval is stopped for 2.0S and lasts for 30min every 3.0S of ultrasonic oscillation time in a constant temperature environment of 25 ℃.
The invention is further configured to: the NiCo2O4The precursor material contained 0.475g of NiCl2·6H2O, 0.950g of CoCl2·6H2O and 0.900g of urea.
The invention is further configured to: the NiCo2O4The precursor material contained 0.580g of Ni (NO)3)2·6H2O, 1.160g of Co (NO)3)2·6H2O and 0.900g of urea.
The invention relates to a metal oxide electrode based on a carbon material and a preparation method thereof, wherein the NiFe2O4The preparation method of the/CNTsCOOH composite material comprises the following steps:
A1. preparation of CNTsCOOH suspension: 0.020g of CNTsCOOH is weighed by an electronic balance and put into a 100ml beaker, 50ml of deionized water is added, and ultrasonic dispersion is carried out for 30min, so as to obtain the suspension of the CNTsCOOH.
A2. Addition of NiFe2O4Precursor: weighing a certain mass of NiFe by using an electronic balance2O4Adding the precursor into the CNTsCOOH suspension liquid which is dispersed by ultrasonic, installing a stirring paddle, and stirring for 30min by using an electric stirrer until the medicine is dissolved;
A3. carrying out hydrothermal reaction: after stirring, pouring reactants into a polytetrafluoroethylene lining of a reaction kettle, washing the reactants which are not poured out of a beaker with 10ml of deionized water, pouring the reactants into the lining, putting the reactants into a hydrothermal reaction kettle, screwing down a cover, and putting the reactants into a forced air drying oven for constant temperature reaction for 8 hours at 120 ℃;
A4. after the reaction is finished, taking the reaction kettle out of the air-blast drying box, and naturally cooling;
A5. and (3) suction filtration: repeatedly washing the cooled reactant with deionized water for 3 times to remove unreacted ions;
A6. after the suction filtration is finished, putting the washing product on the filter membrane into a clean and dry culture dish, wrapping the opening with an aluminum foil, pricking a proper amount of small holes on the aluminum foil to prevent pollution, putting the culture dish into a forced air drying oven, and drying for 8 hours at the temperature of below 100 ℃;
A7. after the sample is dried, the sample is ground into powder by an agate mortar and then is filled into a plastic package bag, and a label is attached and is placed into a drying vessel.
The invention is further configured to: and B, the ultrasonic dispersion in the step A1 is that the oscillation time interval is 3.0s per ultrasonic oscillation time and 2.0s per ultrasonic oscillation time in a constant temperature environment of 25 ℃, and the ultrasonic dispersion lasts for 30 min.
The invention is further configured to: the NiFe2O4The precursor material contained 0.808g Fe (NO)3)3·6H2O, 0.288g of Ni (NO)3)2·6H2O and 0.708g HMT.
In conclusion, the invention has the following beneficial effects:
the invention relates to a metal oxide electrode based on a carbon material and a preparation method thereof, which adopts NiFe for solving the problem of low specific volume of a carbon nano tube2O4The surface of the material is treated to increase the specific surface area, improve the capacitance and improve the multiplying power characteristic. In addition, NiCo is introduced for the problem of poor conductivity due to stacking of graphene sheet layers2O4And graphene interlayer is inserted and coated, so that the conductivity of the electrode material is improved. Three electrodes (carbon electrode, metal oxide electrode and conductive polymer electrode) of the super capacitor are respectively long, the advantage of one electrode is used for making up the disadvantage of the other electrode, a composite material is formed, and the performance of the electrode material is improved.
Drawings
FIG. 1 isThe invention prepares NiCo2O4Schematic representation of the principle of the/GO composite;
FIG. 2 is a schematic representation of the preparation of NiCo according to the invention2O4Another schematic representation of the/GO composite;
FIG. 3 shows the preparation of NiFe according to the present invention2O4Schematic diagram of the/CNTsCOOH composite material.
Detailed Description
In order that those skilled in the art will better understand the novel teachings of the present invention, preferred embodiments of the present invention are described below with reference to specific examples, but it should be understood that these descriptions are only intended to further illustrate the features and advantages of the present invention, and not to limit the patent claims of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention will be further described with reference to the accompanying drawings and preferred embodiments.
Referring to FIGS. 1 to 3, the present example relates to a carbon material-based metal oxide electrode comprising NiCo prepared by hydrothermal synthesis2O4/GO composite material and NiFe prepared by hydrothermal synthesis method2O4a/CNTsCOOH composite material, and combining the two composite materials; the combination mode is made of NiFe2O4Insertion of/CNTsCOOH composite into NiCo2O4The layers of/GO form a three-dimensional mesoporous structure.
The invention relates to a metal oxide electrode based on a carbon material and a preparation method thereof, wherein the NiCo is2O4The preparation steps of the/GO composite material are as follows:
s1, preparing GO suspension: weighing 0.100g of GO by using an electronic balance, putting the GO into a 100ml beaker, adding 50ml of deionized water, and performing ultrasonic dispersion for 30min to obtain a GO suspension;
s2, adding NiCo2O4Precursor: weighing NiCo with a certain mass by using an electronic balance2O4Precursor materials added to ultrasonically dispersed GO suspensionsIn the liquid, a stirring paddle is installed, and the liquid is stirred for 30min by an electric stirrer until the medicine is dissolved;
s3, carrying out hydrothermal reaction: after stirring, pouring reactants into a polytetrafluoroethylene lining, washing the reactants which are not poured out of a beaker with 10ml of deionized water, pouring the reactants into the lining, putting the reactants into a hydrothermal reaction kettle, screwing down a cover, and putting the reactants into an air-blast drying oven for constant-temperature reaction for 8 hours at 120 ℃;
s4, after the reaction is finished, taking the reaction kettle out of the air-blast drying box, and naturally cooling;
s5, suction filtration: repeatedly washing the cooled reactant with deionized water for 3 times to remove unreacted ions;
s6, after the suction filtration is finished, putting a washing product on the filter membrane into a clean and dry culture dish, wrapping an opening with an aluminum foil, pricking a proper amount of small holes on the aluminum foil to prevent pollution, putting the culture dish into a blast drying oven, and drying for 12 hours at 70 ℃;
s7, after the sample is dried, grinding the sample into powder by using an agate mortar, putting the powder into a 30ml corundum crucible, and roasting the powder for 2 hours in a muffle furnace at the temperature of below 400 ℃;
s8, after roasting is finished, taking out the crucible, cooling at room temperature, filling a roasted product in the crucible into a plastic package bag after cooling, attaching a label, and putting the product into a drying dish.
Further, the ultrasonic dispersion in the step S1 is performed at a constant temperature of 25 ℃ for 3.0S per ultrasonic oscillation time, and the oscillation stopping interval time is 2.0S and lasts for 30 min.
Further, said NiCo2O4The precursor material contained 0.475g of NiCl2·6H2O, 0.950g of CoCl2·6H2O and 0.900g of urea or 0.580g of Ni (NO)3)2·6H2O, 1.160g of Co (NO)3)2·6H2O and 0.900g of urea.
The invention relates to a metal oxide electrode based on a carbon material and a preparation method thereof, wherein the NiFe2O4The preparation method of the/CNTsCOOH composite material comprises the following steps:
A1. preparation of CNTsCOOH suspension: 0.020g of CNTsCOOH is weighed by an electronic balance and put into a 100ml beaker, 50ml of deionized water is added, and ultrasonic dispersion is carried out for 30min, so as to obtain the suspension of the CNTsCOOH.
A2. Addition of NiFe2O4Precursor: weighing a certain mass of NiFe by using an electronic balance2O4Adding the precursor into the CNTsCOOH suspension liquid which is dispersed by ultrasonic, installing a stirring paddle, and stirring for 30min by using an electric stirrer until the medicine is dissolved;
A3. carrying out hydrothermal reaction: after stirring, pouring reactants into a polytetrafluoroethylene lining of a reaction kettle, washing the reactants which are not poured out of a beaker with 10ml of deionized water, pouring the reactants into the lining, putting the reactants into a hydrothermal reaction kettle, screwing down a cover, and putting the reactants into a forced air drying oven for constant temperature reaction for 8 hours at 120 ℃;
A4. after the reaction is finished, taking the reaction kettle out of the air-blast drying box, and naturally cooling;
A5. and (3) suction filtration: repeatedly washing the cooled reactant with deionized water for 3 times to remove unreacted ions;
A6. after the suction filtration is finished, putting the washing product on the filter membrane into a clean and dry culture dish, wrapping the opening with an aluminum foil, pricking a proper amount of small holes on the aluminum foil to prevent pollution, putting the culture dish into a forced air drying oven, and drying for 8 hours at the temperature of below 100 ℃;
A7. after the sample is dried, the sample is ground into powder by an agate mortar and then is filled into a plastic package bag, and a label is attached and is placed into a drying vessel.
Further, the ultrasonic dispersion in the step A1 is that the oscillation time interval is 2.0s per 3.0s of ultrasonic oscillation under the constant temperature environment of 25 ℃, and lasts for 30 min.
Further, the NiFe2O4The precursor material contained 0.808g Fe (NO)3)3·6H2O, 0.288g of Ni (NO)3)2·6H2O and 0.708g HMT.
The invention relates to a metal oxide electrode based on a carbon material and a preparation method thereof, which adopts NiFe for solving the problem of low specific volume of a carbon nano tube2O4The surface of the material is treated to increase the specific surface area, increase the capacitance and improve the capacitance by timesRate characteristics. In addition, NiCo is introduced for the problem of poor conductivity due to stacking of graphene sheet layers2O4And graphene interlayer is inserted and coated, so that the conductivity of the electrode material is improved. Three electrodes (carbon electrode, metal oxide electrode and conductive polymer electrode) of the super capacitor are respectively long, the advantage of one electrode is used for making up the disadvantage of the other electrode, a composite material is formed, and the performance of the electrode material is improved.
Unless otherwise specified, in the present invention, if there is an orientation or positional relationship indicated by terms of "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc., based on the orientation or positional relationship actually shown, it is only for convenience of describing the present invention and simplifying the description, rather than to indicate or imply that the device or element so referred to must have a particular orientation, be constructed and operated in a particular orientation, therefore, the terms describing orientation or positional relationship in the present invention are for illustrative purposes only, and should not be construed as limiting the present patent, it is possible for those skilled in the art to combine the embodiments and understand the specific meanings of the above terms according to specific situations.
Unless expressly stated or limited otherwise, the terms "disposed," "connected," and "connected" are used broadly and encompass, for example, being fixedly connected, detachably connected, or integrally connected; the connection may be direct or indirect via an intermediate medium, and may be a communication between the two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (1)
1. A method for preparing a metal oxide electrode based on a carbon material is characterized in that: the electrode comprises a NiCo2O4/GO composite material prepared by a hydrothermal synthesis method and a NiFe2O4/CNTsCOOH composite material prepared by the hydrothermal synthesis method, and the two composite materials are combined; the combination mode is that the NiFe2O4/CNTsCOOH composite material is inserted between the sheets of NiCo2O4/GO to form a three-dimensional mesoporous structure;
the preparation steps of the NiCo2O4/GO composite material are as follows: s1, preparing GO suspension: weighing 0.100g of GO by using an electronic balance, putting the GO into a 100ml beaker, adding 50ml of deionized water, and performing ultrasonic dispersion for 30min to obtain a GO suspension;
s2, adding NiCo2O4 precursor: weighing a certain mass of NiCo2O4 precursor substance by using an electronic balance, adding the precursor substance into the GO suspension liquid which is well dispersed by ultrasonic, installing a stirring paddle, and stirring for 30min by using an electric stirrer until the medicine is dissolved;
s3, carrying out hydrothermal reaction: after stirring, pouring reactants into a polytetrafluoroethylene lining, washing the reactants which are not poured out of a beaker with 10ml of deionized water, pouring the reactants into the lining, putting the reactants into a hydrothermal reaction kettle, screwing down a cover, and putting the reactants into an air-blast drying oven for constant-temperature reaction for 8 hours at 120 ℃;
s4, after the reaction is finished, taking the reaction kettle out of the air-blast drying box, and naturally cooling;
s5, suction filtration: repeatedly washing the cooled reactant with deionized water for 3 times to remove unreacted ions;
s6, after the suction filtration is finished, putting a washing product on the filter membrane into a clean and dry culture dish, wrapping an opening with an aluminum foil, pricking a proper amount of small holes on the aluminum foil to prevent pollution, putting the culture dish into a blast drying oven, and drying for 12 hours at 70 ℃;
s7, after the sample is dried, grinding the sample into powder by using an agate mortar, putting the powder into a 30ml corundum crucible, and roasting the powder for 2 hours in a muffle furnace at the temperature of below 400 ℃;
s8, after roasting is finished, taking out the crucible, cooling at room temperature, filling a roasted product in the crucible into a plastic package bag after cooling, attaching a label, and putting the product into a drying dish;
the ultrasonic dispersion in the step S1 is that the oscillation interval time is stopped for 2.0S and lasts for 30min every 3.0S of ultrasonic oscillation time in a constant temperature environment at 25 ℃;
the NiCo2O4 precursor material comprises 0.475g of NiCl 2.6H2O, 0.950g of CoCl 2.6H2O and 0.900g of urea;
the preparation steps of the NiFe2O4/CNTsCOOH composite material are as follows: A1. preparation of CNTsCOOH suspension: weighing 0.020g of CNTsCOOH by using an electronic balance, putting the CNTsCOOH into a 100ml beaker, adding 50ml of deionized water, and performing ultrasonic dispersion for 30min to obtain a CNTsCOOH suspension;
A2. addition of NiFe2O4 precursor: weighing a certain mass of NiFe2O4 precursor substance by using an electronic balance, adding the precursor substance into the CNTsCOOH suspension liquid which is dispersed by ultrasound, installing a stirring paddle, and stirring for 30min by using an electric stirrer until the medicine is dissolved;
A3. carrying out hydrothermal reaction: after stirring, pouring reactants into a polytetrafluoroethylene lining of a reaction kettle, washing the reactants which are not poured out of a beaker with 10ml of deionized water, pouring the reactants into the lining, putting the reactants into a hydrothermal reaction kettle, screwing down a cover, and putting the reactants into a forced air drying oven for constant temperature reaction for 8 hours at 120 ℃;
A4. after the reaction is finished, taking the reaction kettle out of the air-blast drying box, and naturally cooling;
A5. and (3) suction filtration: repeatedly washing the cooled reactant with deionized water for 3 times to remove unreacted ions;
A6. after the suction filtration is finished, putting the washing product on the filter membrane into a clean and dry culture dish, wrapping the opening with an aluminum foil, pricking a proper amount of small holes on the aluminum foil to prevent pollution, putting the culture dish into a forced air drying oven, and drying for 8 hours at the temperature of below 100 ℃;
A7. after the sample is dried, grinding the sample into powder by using an agate mortar, then filling the powder into a plastic package bag, attaching a label, and putting the label into a drying vessel;
the ultrasonic dispersion in the step A1 is that the ultrasonic oscillation time is 3.0s per time, the oscillation stopping interval time is 2.0s per time and lasts for 30min under the constant temperature environment of 25 ℃;
the NiFe2O4 precursor material contains 0.808g of Fe (NO3) 3.6H 2O, 0.288g of Ni (NO3) 2.6H 2O and 0.708g of HMT.
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