CN111463022A - Preparation method of cobalt molybdenum oxide/nickel cobalt phosphide composite material - Google Patents
Preparation method of cobalt molybdenum oxide/nickel cobalt phosphide composite material Download PDFInfo
- Publication number
- CN111463022A CN111463022A CN202010211023.2A CN202010211023A CN111463022A CN 111463022 A CN111463022 A CN 111463022A CN 202010211023 A CN202010211023 A CN 202010211023A CN 111463022 A CN111463022 A CN 111463022A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- nickel
- composite material
- salt
- molybdenum oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5805—Phosphides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a cobalt-molybdenum oxide/nickel-cobalt phosphide composite material, which comprises the steps of mixing and stirring molybdenum salt and a solvent, adding nickel salt and cobalt salt, and magnetically stirring to form a transparent solution; then moving the mixture into the lining of a polytetrafluoroethylene reaction kettle, and obliquely placing a piece of foamed nickel with the surface oxide layer removed; heating and reacting the reaction kettle for 8 hours in a sealed manner, cooling, taking out the precursor-loaded foam nickel, and respectively and crossly washing the foam nickel in deionized water and absolute ethyl alcohol to obtain a precursor; drying the obtained precursor in a vacuum drying oven; then placing the phosphorus source and a phosphorus source in a tubular furnace for low-temperature phosphorization, and introducing argon protective gas, wherein the temperature of the low-temperature phosphorization is 250-450 ℃, and the heat preservation time is 1-4 h; and respectively cleaning and drying the product in deionized water and absolute ethyl alcohol to obtain the cobalt-molybdenum oxide/nickel-cobalt phosphide composite material. The method has the advantages of simple operation, relatively mild synthesis conditions, energy consumption saving, cheap materials, environmental protection and the like.
Description
Technical Field
The invention relates to a preparation method of a cobalt molybdenum oxide/nickel cobalt phosphide composite material, and particularly relates to the technical field of electrocatalytic materials of clean energy.
Background
With the consumption of traditional non-renewable resources (such as coal, oil, natural gas and the like) and environmental pollution caused by the traditional non-renewable resources, the sustainable development of the environment and the society is damaged and restricted. New energy sources, mainly including nuclear energy, wind energy, solar energy and the like, are developed by various countries. However, due to factors such as seasonal changes and sunshine duration, the problems of intermittence, uncontrollable distribution, uneven distribution and the like of new energy are caused, so that the huge application potential of the new energy is limited, and a large amount of energy is wasted. Therefore, developing an energy storage system with high efficiency, rapidness and low cost to effectively collect and store the energy for recycling is a core problem to be solved at present.
A super capacitor (i.e., an electrochemical capacitor) is a novel electrochemical energy storage device that can be charged and discharged rapidly. The basic structure of the super capacitor mainly comprises an electrode material, electrolyte, a diaphragm and an auxiliary material. In the super capacitor, the electrochemical active substance on the surface of the electrode is the most critical component in the device, and the type and the characteristics of the electrode material greatly determine the overall performance and the application prospect of the device.
Electrode materials of supercapacitors can be divided into two main categories according to the energy storage mechanism: one is an electric double layer electrode material using surface area and pore channel for physical adsorption, such as carbon material, metal organic frame, etc.; another class utilizes redox active pseudocapacitive materials such as metal oxides, metal hydroxides, conducting polymers, phosphides, nitrides and sulfides. Among these catalysts, the transition metal phosphides (CoP )2、Ni2P、Ni12P5Etc.) has better mechanical strength and electricityChemical conductivity and chemical stability. Because the atomic radius (0.109 nm) of phosphorus is larger, phosphide generally consists of a triangular prism structure, and meanwhile, the prisms are stacked to form an anisotropic growth structure, the special structure can cause metal phosphide to have more coordination unsaturated surface atomic numbers, and if other oxides with excellent performance are compounded to form a composite material, the transition metal phosphide composite material has higher inherent electrochemical activity.
At present, transition metal phosphide is prepared mainly by a high-energy ball milling method, a temperature programmed reduction method and a thermal decomposition method. Chou topic group uses high energy ball milling method ([ 2 ]]Li W J, Yang Q R, Chou S L, et al. Cobaltphosphide as a new anode material for sodium storage[J]Journal of Power sources, 2015, 294: 627-. Wang project group reduction by temperature programmed method ([ 3 ]]Bai Y, Zhang H, Liu L, et al. Tunable andspecific formation of C@NiCoP peapods with enhanced HER activity and lithiumstorage performance[J]Chemistry-A European Journal, 2016, 22(3): 1021-1029.) A legume-like NiCoP @ C was prepared by introducing a reducing gas H under high temperature conditions2Has certain dangerousness; yang group of subjects was obtained by pyrolysis method ([ 4 ]]Jiang J, Wang C, Liang J, et al.Synthesis of nanorod-FeP@C composites with hysteretic lithiation in lithium-ion batteries[J]Dalton Transactions 2015,44(22): 10297-. Therefore, research and development of efficient and simple preparation methods of transition metal phosphide catalysts are urgently needed.
Disclosure of Invention
At present, the electrode material is mainly prepared by adding a precipitator and a surfactant in the preparation process, and the problems of harsh and complex preparation conditions, high cost, high risk, serious product agglomeration and the like exist. The invention provides a preparation method of a cobalt molybdenum oxide/nickel cobalt phosphide composite material. The method has the advantages of cheap raw materials, simple and safe synthesis method, no need of adding extra precipitator and surfactant, production cost reduction, environmental friendliness, wide application prospect of the prepared cobalt molybdenum oxide/nickel cobalt phosphide composite material in the fields of supercapacitors, lithium ion batteries and the like, and effective overcoming of various defects in the prior art.
The technical scheme of the invention is realized as follows:
a method for preparing cobalt molybdenum oxide/nickel cobalt phosphide composite material, adopt the low-temperature hydrothermal-phosphorization method, do not need to add precipitant and surfactant active in the reaction, utilize molybdenum salt, nickel salt and cobalt salt and solvent reaction to produce hydroxide ion directly; putting the treated precursor and a phosphorus source into a tubular furnace for low-temperature phosphorization, and introducing argon protective gas to ensure that the active substance directly grows on the nickel foam in situ and is directly used as a working electrode, wherein the preparation method comprises the following specific steps:
1) 123.6mg of molybdenum salt are mixed with solvent (V)Ethanol：VDeionized water= 4: 3) mixing, and magnetically stirring at 360rpm/min for 30min to form transparent solution;
2) adding 291mg of nickel salt and 291mg of cobalt salt into the mixture obtained in the step (1), and magnetically stirring the mixture for 30min at the rotating speed of 360rpm/min to form a transparent solution;
C) transferring the transparent solution into the inner liner of a polytetrafluoroethylene reaction kettle, and obliquely placing a piece of foamed nickel (2 × 4 cm) for removing the surface oxidation layer2）；
D) Sealing the reaction kettle, heating to 120-160 ℃ for reaction for 8 hours, cooling to room temperature, taking out the precursor-loaded foam nickel, and respectively and alternately washing in deionized water and absolute ethyl alcohol for 3-6 times; obtaining a precursor;
E) drying the precursor obtained in the step D) in a vacuum drying oven at the temperature of 40-70 ℃ for 6-20 h;
F) placing the precursor obtained in the step E) and a phosphorus source in a tubular furnace for low-temperature phosphorization, and introducing nitrogen protective gas, wherein the phosphorus source is placed in an upper air port; the temperature of low-temperature phosphorization is 250-450 ℃, and the heat preservation time is 1-4 h;
G) and respectively cleaning the phosphated product in deionized water and absolute ethyl alcohol for 3-6 times, and drying in a vacuum drying oven for 6-20 hours to obtain the cobalt-molybdenum oxide/nickel-cobalt phosphide composite material.
The molybdenum salt in the step A) is one or a mixture of more of ammonium molybdate, sodium molybdate, molybdenum nitrate and molybdenum chloride; the solvent is one or a mixture of anhydrous ethanol, ethylenediamine, glycol and deionized water.
The nickel salt in the step B) is one or a mixture of more of nickel acetylacetonate, nickel sulfate, nickel nitrate and nickel chloride; the cobalt salt is one or a mixture of more of cobalt acetylacetonate, cobalt sulfate, cobalt nitrate and cobalt chloride.
The phosphorus source in the step F) is one or a mixture of sodium hypophosphite, ammonium dihydrogen phosphate and diammonium hydrogen phosphate. The mol ratio of the usage amount of the phosphorus source to the nickel-cobalt precursor is 1: 1-10: 1 during low-temperature phosphorization.
The prepared cobalt molybdenum oxide/nickel cobalt phosphide composite material is used for preparing electrode materials of super capacitors and lithium ion batteries. Can also be used for preparing hydrogen by electrolyzing water, preparing hydrogen by photocatalysis and preparing H by photocatalysis2O2And solar cells.
The invention has the advantages that:
(1) the cobalt molybdenum oxide/nickel cobalt phosphide composite material synthesized by adopting a low-temperature hydrothermal-phosphating method has high crystallinity and has ultrathin nano sheets and a nano rod structure;
(2) in the process of synthesizing the precursor through the hydrothermal reaction, a precipitator and a surfactant are not required to be added, so that the production cost is reduced, and the environment is better embodied;
(3) according to the invention, nickel foam with a three-dimensional porous net shape is used as a substrate to directly grow an active material in situ, the roughness of the surface of an electrode is changed, the actual contact area of the electrode material and an electrolyte is increased, and the activity of the electrode material of the super capacitor is obviously improved;
(4) the invention has simple and safe operation, low cost and good repeatability.
The invention effectively overcomes the problems of harsh and complex preparation conditions, high cost, high risk, serious product agglomeration and the like in the prior art. The prepared cobalt-molybdenum oxide/nickel-cobalt phosphide composite material has wide application prospect in the fields of super capacitors, lithium ion batteries and the like.
Drawings
FIG. 1(a) is an SEM image of a cobalt molybdenum oxide/nickel cobalt phosphide composite material prepared in example 1;
(b) SEM images of cobalt molybdenum oxide/nickel cobalt phosphide composites prepared for comparative examples;
FIG. 2 is an XRD pattern of a cobalt molybdenum oxide/nickel cobalt phosphide composite material prepared in comparative example and example 1;
fig. 3 is a charge and discharge curve of the cobalt molybdenum oxide/nickel cobalt phosphide composite material prepared in the comparative example and example 1 in 6M potassium hydroxide solution.
Detailed Description
The invention is explained in further detail below with reference to specific embodiments and with reference to the drawings.
[ COMPARATIVE EXAMPLES ]
The preparation process of the cobalt molybdenum oxide/nickel cobalt phosphide composite material comprises the following steps:
(1) soaking nickel foam in acetone for 10min, then soaking in 2M dilute hydrochloric acid solution for 10min to remove an oxide layer on the surface, washing with a large amount of deionized water, and vacuum drying;
(2) 291mg of nickel nitrate hexahydrate, 291mg of cobalt nitrate hexahydrate, 123.6mg of ammonium molybdate tetrahydrate were dissolved in 35m L of deionized water and an anhydrous ethanol solution (V)Water (W)：VEthanol= 4: 3) magnetically stirring the mixture for 30min at the rotating speed of 360rpm/min to form transparent solution;
(3) pouring the solution obtained in the step (2) into a reaction kettle inner liner with the capacity of 50m L, and obliquely placing a piece of processed foamed nickel (2 × 4 cm)2) Preserving the heat for 4 hours at the temperature of 140 ℃, and naturally cooling to room temperature to obtain a precursor;
(4) respectively carrying out cross washing on the precursor obtained in the step (3) by using deionized water and absolute ethyl alcohol for 3-6 times, and drying the washed product in a vacuum drying oven at 60 ℃ for 6 hours;
(5) placing the dried precursor in the step (4) and weighed sodium hypophosphite in a quartz tube, placing the sodium hypophosphite in an upper air inlet, heating the tube furnace from room temperature to 350 ℃ at the heating speed of 3 ℃/min, and keeping the temperature for 90min, wherein the whole calcining process is carried out in the argon protection atmosphere;
(6) naturally cooling to room temperature, washing the obtained black product in deionized water and absolute ethyl alcohol for 3 times respectively, and then drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain a black final product as a comparison.
[ example 1 ]
The preparation process of the cobalt molybdenum oxide/nickel cobalt phosphide composite material comprises the following steps:
(1) soaking nickel foam in acetone for 10min, then soaking in 2M dilute hydrochloric acid solution for 10min to remove an oxide layer on the surface, washing with a large amount of deionized water, and vacuum drying;
(2) 291mg of nickel chloride, 291mg of cobalt chloride, 123.6mg of molybdenum chloride were dissolved in 35m L of deionized water and an absolute ethanol solution (V)Water (W)：VEthanol= 4: 3) magnetically stirring the mixture for 30min at the rotating speed of 360rpm/min to form transparent solution;
(3) pouring the solution obtained in the step (2) into a reaction kettle inner liner with the capacity of 50m L, and obliquely placing a piece of processed foamed nickel (2 × 4 cm)2) Preserving the heat for 8 hours at the temperature of 140 ℃, and naturally cooling to room temperature to obtain a precursor;
(4) respectively carrying out cross washing on the precursor obtained in the step (4) by using deionized water and absolute ethyl alcohol for 3-6 times, and drying the washed product in a vacuum drying oven at 60 ℃ for 6 hours;
(5) placing the dried precursor in the step (5) and weighed sodium hypophosphite in a quartz tube, placing the sodium hypophosphite in an air inlet, heating the tube furnace from room temperature to 350 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 120min, wherein the whole calcination process is performed at N2The preparation is carried out in a protective atmosphere;
(6) and naturally cooling to room temperature, respectively cleaning the obtained black product for 3 times by using deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain a black final product, thereby finally obtaining the cobalt molybdenum oxide/nickel cobalt phosphide composite material.
[ example 2 ]
(1) Soaking nickel foam in acetone for 10min, then soaking in 2M dilute hydrochloric acid solution for 10min to remove an oxide layer on the surface, washing with a large amount of deionized water, and vacuum drying;
(2) 291mg of nickel nitrate hexahydrate, 291mg of cobalt nitrate hexahydrate, 123.6mg of molybdenum chloride were dissolved in 35m L of deionized water and an absolute ethanol solution (V)Water (W)：VEthanol= 4: 3) magnetically stirring the mixture for 30min at the rotating speed of 360rpm/min to form transparent solution;
(3) pouring the solution obtained in the step (2) into a reaction kettle inner liner with the capacity of 50m L, and obliquely placing a piece of processed foamed nickel (2 × 4 cm)2) Preserving the heat for 8 hours at the temperature of 120 ℃, and naturally cooling to room temperature to obtain a precursor;
(4) respectively carrying out cross washing on the precursor obtained in the step (3) by using deionized water and absolute ethyl alcohol for 3-6 times, and drying the washed product in a vacuum drying oven at 60 ℃ for 6 hours;
(5) placing the dried precursor in the step (4) and weighed sodium hypophosphite in a quartz tube, placing the sodium hypophosphite in an upper air inlet, heating the tube furnace from room temperature to 350 ℃ at the heating speed of 3 ℃/min, and keeping the temperature for 150min, wherein the whole calcining process is carried out in the argon protection atmosphere;
(6) and naturally cooling to room temperature, respectively cleaning the obtained black product for 3 times by using deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain a black final product, thereby finally obtaining the cobalt molybdenum oxide/nickel cobalt phosphide composite material.
[ example 3 ]
(1) Soaking nickel foam in acetone for 10min, then soaking in 2M dilute hydrochloric acid solution for 10min to remove an oxide layer on the surface, washing with a large amount of deionized water, and vacuum drying;
(2) 291mg of nickel nitrate, 291mg of cobalt nitrate, 123.6mg of molybdenum nitrate were dissolved in 35m L of deionized water and an absolute ethanol solution (V)Water (W)：VEthanol= 4: 3) in the rotating speed of 360rpm/minMagnetically stirring for 30min to form transparent solution;
(3) pouring the solution obtained in the step (2) into a reaction kettle inner liner with the capacity of 50m L, and obliquely placing a piece of processed foamed nickel (2 × 4 cm)2) Preserving the heat for 8 hours at 160 ℃, and naturally cooling to room temperature to obtain a precursor;
(4) respectively carrying out cross washing on the precursor obtained in the step (3) by using deionized water and absolute ethyl alcohol for 3-6 times, and drying the washed product in a vacuum drying oven at 60 ℃ for 6 hours;
(5) placing the dried precursor in the step (4) and weighed sodium hypophosphite in a quartz tube, placing the sodium hypophosphite in an upper air inlet, heating the tube furnace from room temperature to 350 ℃ at the heating speed of 3 ℃/min, and keeping the temperature for 180min, wherein the whole calcining process is carried out in the argon protection atmosphere;
(6) and naturally cooling to room temperature, respectively cleaning the obtained black product for 3 times by using deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain a black final product, thereby finally obtaining the cobalt molybdenum oxide/nickel cobalt phosphide composite material.
[ example 4 ]
(1) Soaking nickel foam in acetone for 10min, then soaking in 2M dilute hydrochloric acid solution for 10min to remove an oxide layer on the surface, washing with a large amount of deionized water, and vacuum drying;
(2) 291mg of nickel sulfate, 291mg of cobalt sulfate, 123.6mg of sodium molybdate were dissolved in 35m L of deionized water and an absolute ethanol solution (V)Water (W)：VEthanol= 4: 3) magnetically stirring the mixture for 30min at the rotating speed of 360rpm/min to form transparent solution;
(3) pouring the solution obtained in the step (2) into a reaction kettle inner liner with the capacity of 50m L, and obliquely placing a piece of processed foamed nickel (2 × 4 cm)2) Preserving the heat for 10 hours at the temperature of 140 ℃, and naturally cooling to room temperature to obtain a precursor;
(4) respectively carrying out cross washing on the precursor obtained in the step (3) by using deionized water and absolute ethyl alcohol for 3-6 times, and drying the washed product in a vacuum drying oven at 60 ℃ for 6 hours;
(5) placing the dried precursor in the step (4) and weighed sodium hypophosphite in a quartz tube, placing the sodium hypophosphite in an air inlet, heating the tube furnace from room temperature to 250 ℃ at the heating speed of 3 ℃/min, and keeping the temperature for 240min, wherein the whole calcining process is carried out in the argon protection atmosphere;
(6) and naturally cooling to room temperature, respectively cleaning the obtained black product for 3 times by using deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain a black final product, thereby finally obtaining the cobalt molybdenum oxide/nickel cobalt phosphide composite material.
[ example 5 ]
(1) Soaking nickel foam in acetone for 10min, then soaking in 2M dilute hydrochloric acid solution for 10min to remove an oxide layer on the surface, washing with a large amount of deionized water, and vacuum drying;
(2) 291mg of nickel acetylacetonate, 291mg of acetylacetone, 123.6mg of ammonium molybdate tetrahydrate were dissolved in 35m L of deionized water and an anhydrous ethanol solution (V)Water (W)：VEthanol= 4: 3) magnetically stirring the mixture for 30min at the rotating speed of 360rpm/min to form transparent solution;
(3) pouring the solution obtained in the step (2) into a reaction kettle inner liner with the capacity of 50m L, and obliquely placing a piece of processed foamed nickel (2 × 4 cm)2) Preserving the heat for 10 hours at the temperature of 120 ℃, and naturally cooling to room temperature to obtain a precursor;
(4) respectively carrying out cross washing on the precursor obtained in the step (3) by using deionized water and absolute ethyl alcohol for 3-6 times, and drying the washed product in a vacuum drying oven at 60 ℃ for 6 hours;
(5) placing the dried precursor in the step (4) and weighed sodium hypophosphite in a quartz tube, placing the sodium hypophosphite in an upper air inlet, heating the temperature of the tube furnace from room temperature to 450 ℃ at the heating speed of 3 ℃/min, and keeping the temperature for 90min, wherein the whole calcining process is carried out in the argon protection atmosphere;
(6) and naturally cooling to room temperature, respectively cleaning the obtained black product for 3 times by using deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain a black final product, thereby finally obtaining the cobalt molybdenum oxide/nickel cobalt phosphide composite material.
Inventive example 1 and comparativeThe shapes of the cobalt molybdenum oxide/nickel cobalt phosphide composite material with the hydrothermal heat preservation time of 4h and 8h are respectively shown in fig. 1(a) and (b), and the Co in the solution can be seen from fig. 1(a)2+、Ni2+、Mo6+When the reaction occurs, the foam nickel with rough and porous surface is nucleated, the formed nano thin sheet and nano rod cover the surface of the foam nickel, and the diameter of the nano rod is about 1.5 microns; FIG. 1 (b) shows Co in solution2+、Ni2+、Mo6+When the reaction occurs, the nickel foam with rough and porous surface is nucleated, the formed nano thin sheets and nano rods firstly uniformly cover the surface of the nickel foam, and then ultrathin nano flowers are formed on the top of the rod to reduce the surface energy, wherein the thickness of petals is 40-60nm, and the diameter of the nano rods is about 1.2 microns. The X-ray diffraction patterns of the cobalt molybdenum oxide/nickel cobalt phosphide composite materials prepared in the embodiment 1 and the comparative example with the hydrothermal heat preservation time of 4h and 8h are shown in figure 2, and it can be clearly seen in the figure that the prepared samples are cobalt molybdenum oxide, nickel cobalt phosphide and nickel foam, the crystallinity of the sample with the hydrothermal heat preservation time of 8h is better than that of the sample with the hydrothermal heat preservation time of 4h, and the diffraction peak of the nickel cobalt phosphide is not obvious due to the fact that the diffraction peak of the nickel cobalt phosphide is too strong. Then, the prepared material is subjected to electrochemical tests, as shown in fig. 3, in an alkaline solution (6M KOH), when the current density of the cobalt molybdenum oxide/nickel cobalt phosphide composite material with the hydrothermal insulation time of 8 hours is 1A/g, the cobalt molybdenum oxide/nickel cobalt phosphide composite material with the discharge time longer than the hydrothermal insulation time of 4 hours has higher specific capacitance. In summary, the cobalt molybdenum oxide/nickel cobalt phosphide composite material with the hydrothermal insulation time of 8 hours (example 1) has a smaller morphology and an ultra-large specific surface area compared with the cobalt molybdenum oxide/nickel cobalt phosphide composite material with the hydrothermal insulation time of 4 hours (comparative example), and can effectively reduce the internal resistance of the material.
The foregoing detailed description of the embodiments of the present invention is provided for illustration only and not for the purpose of limiting the invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention.
Claims (5)
1. A method for preparing cobalt molybdenum oxide/nickel cobalt phosphide composite material, adopt the low-temperature hydrothermal-phosphorization method, do not need to add extra precipitant and surfactant active in the reaction, utilize molybdenum salt, nickel salt and cobalt salt and solvent reaction to produce hydroxide ion directly; the treated precursor and a phosphorus source are placed in a tubular furnace for low-temperature phosphorization, argon protective gas is introduced, active substances grow in situ on foamed nickel and can be directly used as a working electrode, and the method is characterized in that: the preparation method comprises the following specific steps:
123.6mg of molybdenum salt are mixed with solvent (V)Ethanol：VDeionized water= 4: 3) mixing, and magnetically stirring at 360rpm/min for 30min to form transparent solution;
adding 291mg of nickel salt and 291mg of cobalt salt into the mixture obtained in the step (1), and magnetically stirring the mixture for 30min at the rotating speed of 360rpm/min to form a transparent solution;
transferring the transparent solution into the inner liner of a polytetrafluoroethylene reaction kettle, and obliquely placing a piece of foamed nickel (2 × 4 cm) for removing the surface oxidation layer2）；
Sealing the reaction kettle, heating to 120-160 ℃ for reaction for 8 hours, cooling to room temperature, taking out the precursor-loaded foam nickel, and respectively and alternately washing in deionized water and absolute ethyl alcohol for 3-6 times; obtaining a precursor;
drying the precursor obtained in the step 4) in a vacuum drying oven at the temperature of 40-80 ℃ for 6-20 h;
placing the precursor obtained in the step 5) and a phosphorus source in a tubular furnace for low-temperature phosphorization, and introducing argon protective gas, wherein the phosphorus source is placed in an upper air port; the temperature of the low-temperature phosphorization is 250-450 ℃, and the heat preservation time is 1-4 h;
and respectively cleaning the phosphated product in deionized water and absolute ethyl alcohol for 3-6 times, and drying in a vacuum drying oven for 6-20 hours to obtain the cobalt-molybdenum oxide/nickel-cobalt phosphide composite material.
2. The method of claim 1, wherein the cobalt molybdenum oxide/nickel cobalt phosphide composite material comprises: the molybdenum salt in the step 1) is one or a mixture of more of ammonium molybdate, sodium molybdate, molybdenum nitrate and molybdenum chloride; the solvent is one or a mixture of anhydrous ethanol, ethylenediamine, glycol and deionized water.
3. The method of claim 1, wherein the cobalt molybdenum oxide/nickel cobalt phosphide composite material comprises: the cobalt salt in the step 2) is one or a mixture of more of cobalt acetylacetonate, cobalt sulfate, cobalt nitrate and cobalt chloride; the nickel salt is one or a mixture of more of nickel acetylacetonate, nickel sulfate, nickel nitrate and nickel chloride.
4. The method of claim 1, wherein the cobalt molybdenum oxide/nickel cobalt phosphide composite material comprises: the phosphorus source in the step 6) is one or a mixture of sodium hypophosphite, ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the mol ratio of the usage amount of the phosphorus source to the nickel-cobalt precursor is 1: 1-10: 1 during low-temperature phosphorization.
5. The method of claim 1, wherein the cobalt molybdenum oxide/nickel cobalt phosphide composite material comprises: the prepared cobalt molybdenum oxide/nickel cobalt phosphide composite material is used as an electrocatalytic material for preparing a super capacitor electrode material and a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010211023.2A CN111463022A (en) | 2020-03-24 | 2020-03-24 | Preparation method of cobalt molybdenum oxide/nickel cobalt phosphide composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010211023.2A CN111463022A (en) | 2020-03-24 | 2020-03-24 | Preparation method of cobalt molybdenum oxide/nickel cobalt phosphide composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111463022A true CN111463022A (en) | 2020-07-28 |
Family
ID=71683261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010211023.2A Pending CN111463022A (en) | 2020-03-24 | 2020-03-24 | Preparation method of cobalt molybdenum oxide/nickel cobalt phosphide composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111463022A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112951613A (en) * | 2021-02-01 | 2021-06-11 | 中国科学技术大学 | Electrode material and preparation method and application thereof |
| CN113699552A (en) * | 2021-08-26 | 2021-11-26 | 中南大学 | Cobalt phosphate-molybdenum trioxide composite nanorod array three-dimensional electrode material and preparation method and application thereof |
| CN115010220A (en) * | 2022-06-17 | 2022-09-06 | 南通大学 | Electrode with phosphide and hydroxide heterostructure and preparation method thereof |
| CN115172058A (en) * | 2022-08-01 | 2022-10-11 | 河南大学 | MoP/MoNiP 2 Composite material, preparation method and application thereof |
| CN115440504A (en) * | 2021-06-02 | 2022-12-06 | 重庆三峡学院 | Mo-CoP @ Ni-Fe LDH core-shell hierarchical nanosheet and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7446075B1 (en) * | 2005-08-23 | 2008-11-04 | Uop Llc | Transition metal phosphides and hydrotreating process using the same |
| CN104988536A (en) * | 2015-08-04 | 2015-10-21 | 重庆大学 | Method for preparing high-performance molybdenum-based hydrogen evolution electrode by phosphatizing molybdate precursor |
| CN108671948A (en) * | 2018-05-17 | 2018-10-19 | 上海理工大学 | A kind of preparation method of the flower-shaped nickel cobalt phosphide electrocatalysis material of self-assembling ultrathin |
-
2020
- 2020-03-24 CN CN202010211023.2A patent/CN111463022A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7446075B1 (en) * | 2005-08-23 | 2008-11-04 | Uop Llc | Transition metal phosphides and hydrotreating process using the same |
| CN104988536A (en) * | 2015-08-04 | 2015-10-21 | 重庆大学 | Method for preparing high-performance molybdenum-based hydrogen evolution electrode by phosphatizing molybdate precursor |
| CN108671948A (en) * | 2018-05-17 | 2018-10-19 | 上海理工大学 | A kind of preparation method of the flower-shaped nickel cobalt phosphide electrocatalysis material of self-assembling ultrathin |
Non-Patent Citations (1)
| Title |
|---|
| JINGHUANG LIN.ET AL: ""Bifunctional Electrocatalysts Based on Mo-Doped NiCoP Nanosheet Arrays for Overall Water Splitting"", 《NANO-MICRO LETT.》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112951613A (en) * | 2021-02-01 | 2021-06-11 | 中国科学技术大学 | Electrode material and preparation method and application thereof |
| CN115440504A (en) * | 2021-06-02 | 2022-12-06 | 重庆三峡学院 | Mo-CoP @ Ni-Fe LDH core-shell hierarchical nanosheet and preparation method and application thereof |
| CN113699552A (en) * | 2021-08-26 | 2021-11-26 | 中南大学 | Cobalt phosphate-molybdenum trioxide composite nanorod array three-dimensional electrode material and preparation method and application thereof |
| CN113699552B (en) * | 2021-08-26 | 2022-07-29 | 中南大学 | Cobalt phosphate-molybdenum trioxide composite nanorod array three-dimensional electrode material and preparation method and application thereof |
| CN115010220A (en) * | 2022-06-17 | 2022-09-06 | 南通大学 | Electrode with phosphide and hydroxide heterostructure and preparation method thereof |
| CN115010220B (en) * | 2022-06-17 | 2023-12-01 | 南通大学 | Electrode with phosphide synergistic hydroxide heterostructure and preparation method thereof |
| CN115172058A (en) * | 2022-08-01 | 2022-10-11 | 河南大学 | MoP/MoNiP 2 Composite material, preparation method and application thereof |
| CN115172058B (en) * | 2022-08-01 | 2023-10-10 | 河南大学 | MoP/MoNiP 2 Composite material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111463022A (en) | Preparation method of cobalt molybdenum oxide/nickel cobalt phosphide composite material | |
| CN101817520B (en) | Method for manufacturing carbon microspheres by using waste macromolecules | |
| CN112382515B (en) | Oxygen defect T-Nb 2 O 5-x Preparation method and application | |
| CN110416537A (en) | Lithium titanate composite anode material and preparation method thereof and lithium ion battery | |
| CN112103092B (en) | Metal cation doped cobalt polysulfide/cobalt hydroxide composite material and preparation method and application thereof | |
| CN112234206A (en) | Method for preparing thin-layer graphene/transition metal fluoride composite positive active material by using antibiotic fungi residues | |
| CN111525123A (en) | Cathode material of water-based lithium ion battery and preparation method and application thereof | |
| CN113716550A (en) | Preparation of transition metal layered double-metal hydroxide carbon nanotube composite material and application of composite material in battery | |
| Liu et al. | A more economical choice for the cathode material of Ni-MH batteries with high electrochemical performances: 3D flower-like Ni–Fe LDHs | |
| CN113809286B (en) | Metal Organic Framework (MOF) catalyzed growth carbon nanotube coated nickel-tin alloy electrode material and preparation method and application thereof | |
| CN112435866A (en) | Carbon-coated iron oxide nanorod array material grown on foamed titanium substrate and preparation method thereof | |
| CN112467077A (en) | Universal electrochemical modification preparation method for effectively enhancing electricity storage performance of multiple transition metal oxides | |
| CN109768233B (en) | NiCo of lithium ion battery2S4Preparation method of/graphene composite negative electrode material | |
| CN116812969A (en) | Preparation method of hierarchical pore indium oxide nanotube for lithium ion battery cathode | |
| CN110767960A (en) | Flexible device integrating microbial fuel cell and hybrid supercapacitor, and preparation method and application thereof | |
| CN106207251B (en) | Carbon coating method of hydrothermal lithium iron phosphate | |
| CN111547710B (en) | Graphene-based composite material and preparation method and application thereof | |
| CN113097467B (en) | Preparation method of lithium ion battery composite material with double-layer shell structure | |
| CN111341567B (en) | 3D poplar catkin derived carbon-supported NiCo-LDH nanosheet supercapacitor and preparation method thereof | |
| CN114975933A (en) | Hierarchical slice MnO 2 @Co 3 O 4 @ C flexible composite electrode and preparation method and application thereof | |
| CN114843118A (en) | Electrode composite material GO-C @ M (OH) with hierarchical pores 2 And preparation method and application thereof | |
| CN108963214B (en) | Preparation method of lithium ion battery negative electrode material | |
| Wang et al. | Economic synthesis of sub-micron brick-like Al-MOF with designed pore distribution for lithium-ion battery anodes with high initial Coulombic efficiency and cycle stability | |
| Zhang et al. | Simple Preparation of Co3O4 with a Controlled Shape and Excellent Lithium Storage Performance | |
| CN107068423B (en) | A kind of Preparation method and use of cobalt oxide/graphene/multi-stage porous carbon electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200728 |