CN111668031A - Vanadium nitride-pore carbon nano composite material and preparation method and application thereof - Google Patents

Vanadium nitride-pore carbon nano composite material and preparation method and application thereof Download PDF

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CN111668031A
CN111668031A CN201910165192.4A CN201910165192A CN111668031A CN 111668031 A CN111668031 A CN 111668031A CN 201910165192 A CN201910165192 A CN 201910165192A CN 111668031 A CN111668031 A CN 111668031A
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vanadium
solution
vanadyl
stage calcination
calcination
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曹宏斌
宁朋歌
杨海伦
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Institute of Process Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • C—CHEMISTRY; METALLURGY
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • H—ELECTRICITY
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    • 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
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    • 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
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    • 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
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    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
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    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
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    • Y02E60/10—Energy storage using batteries
    • 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
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    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention relates to a vanadium nitride-porous carbon nano composite material and a preparation method and application thereof, wherein V in a vanadyl solution is extracted by the method, so that the requirement of the preparation process on the purity of vanadium species in the vanadyl solution is lowered, and the cost of the preparation process is lowered; the V species in the vanadium nitride-pore carbon nano composite material prepared by the method mainly exist in the form of vanadium nitride, and the content of the V species can reach 42.5 percent at most.

Description

Vanadium nitride-pore carbon nano composite material and preparation method and application thereof
Technical Field
The invention relates to the field of nano materials, in particular to a vanadium nitride-pore carbon nano composite material and a preparation method and application thereof.
Background
Vanadium nitride is widely applied to the field of energy storage materials due to the remarkable electrochemical specificity and chemical stability of vanadium nitride. However, the material synthesis steps are complex, the conditions are harsh, and the product particle agglomeration is the main problem to be solved by the preparation process. Many nitride (particularly, comprising s-block elements) fabrication processes are reported in the literature to be very sensitive to air and moisture. The presence of these factors can affect the amount of nitride in the product. In order to avoid agglomeration of transition metal nitride, in literature reports, a template (melamine) is usually added during calcination or a vanadium-containing substance is supported on graphene or carbon nanotubes by a hydrothermal method, and then the product is calcined in an ammonia atmosphere; therefore, it develops slower than transition metal oxides and fluorides; meanwhile, the higher raw material cost restricts the further development of the energy storage material.
At present, the synthesis methods of transition metal nitrides mainly fall into the following three categories:
(1) calcining a mixture of a transition metal and carbon in an atmosphere of nitrogen or ammonia; the content of nitride in the product is low;
(2) aminolysis of binary transition metal compounds (chlorides, sulfides, oxides); metal sintering can be avoided;
(3) the transition metal nitride film is prepared by a vapor deposition method. The method is widely applied to the preparation of film products, and the products are nano or micron crystals;
other methods further include: solid state metathesis, solvothermal, sol synthesis, and the like.
Xin Bin Yang et al reported a method of synthesizing vanadium nitride/graphene complexes: which comprises the following steps: (1) 0.2g of amine metavanadate was dissolved in water in a volume ratio of 9: 1: adjusting the pH of the solution to 2-3 by using hydrochloric acid in a mixed solution of ethanol, putting the solution into a 100ml hydrothermal kettle, then adding 30ml of graphene oxide (2mg/ml), and maintaining the hydrothermal kettle at 180 ℃ for 24 hours; (2) calcining the product obtained in the step (1) under the condition of a mixed gas of argon and ammonia gas to finally obtain a vanadium nitride/Graphene Composite (see the documents Wang R, Lang J, Zhang P, et al. fast and Large lithium Storage in 3D ports VN Nanowires-Graphene Composite as a superior and upward High-Performance Hybrid Supercapacitors [ J ]. Advanced functional materials,2015,25(15): 2270-2278); the preparation process is complex, and simultaneously, graphene needs to be added, so that the preparation cost is increased.
CN109205590A discloses a vanadium nitride nanocluster loaded on a 3D carbon foam skeleton and a preparation method thereof, which comprises the following steps: firstly, carbonizing melamine foam to obtain a 3D carbon foam body; step two, immersing the 3D carbon foam body in the step one into the solution A, and carrying out hydrothermal reaction; the solution A is prepared by mixing 10-30 mol/L ammonium metavanadate, 1-10 mol/L hexamethylenetetramine and oxalic acid aqueous solution in the weight ratio of (1-3): (1-4): (1-5) mixing in a volume ratio, and fully stirring to obtain the product; after the reaction is finished and the temperature is cooled to room temperature, the 3D carbon foam body is alternately washed by water and absolute ethyl alcohol, and is frozen and dried to obtain an intermediate product; thirdly, calcining the intermediate product, and cooling to room temperature after the reaction is finished to obtain vanadium nitride nanoclusters loaded on a 3D carbon framework; according to the scheme, only chemically pure ammonium metavanadate can be adopted as the vanadium source, and the preparation process is complex and the cost is high.
CN109280934A discloses a carbon-coated vanadium nitride electrocatalyst, which is prepared by uniformly mixing carbon-rich organic matters as a carbon source, a metal vanadium salt as a vanadium source, urea, ammonium carbonate, ammonium bicarbonate and the like as nitrogen sources by a mechanical method and then calcining the mixture in one step.
Although the above documents disclose some methods for preparing vanadium nitride-carbon nanocomposites, the problems of high preparation cost and low vanadium nitride content in the product still remain, and therefore, the development of a method for preparing vanadium nitride-carbon nanocomposites at low cost is still of great significance.
Disclosure of Invention
The invention aims to provide a vanadium nitride-porous carbon nano composite material and a preparation method and application thereof, wherein V in a vanadyl solution is extracted by extraction, so that the requirement of the preparation process on the purity of vanadium species in the vanadyl solution is reduced, amine substances are used as a carbon source and a nitrogen source in the preparation process, the cost of the preparation process is reduced, and the average particle size of vanadium nitride in the prepared vanadium nitride-porous carbon nano composite material is 2-10nm due to the coordination effect between an amine extractant and the V element, and the vanadium nitride is uniformly distributed on porous carbon.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a vanadium nitride-porous carbon nanocomposite, comprising the steps of:
(1) mixing a mixture of an amine substance, a cyanamide substance and an organic solvent with a vanadyl acid solution to obtain an extract compound;
(2) and (2) calcining the dried extract compound in the step (1) in a non-oxidizing atmosphere to obtain the vanadium nitride-pore carbon nanocomposite.
According to the method, vanadium in the vanadyl acid solution is extracted into the extract compound by adopting an extraction method, the extract compound is dried and then is calcined in a non-oxidizing atmosphere to obtain the vanadium nitride-porous carbon nanocomposite, and the preparation process adopts an extraction mode, so that the purity requirement on vanadium species in the vanadyl acid solution is low in the preparation process, and the cost of the preparation process is reduced; the vanadium nitride content of V species in the vanadium nitride-pore carbon nano composite material prepared by the method can reach 42.5 percent at most.
Preferably, the method for obtaining the extract compound in the step (1) comprises the step of standing the mixed solution or separating the mixed solution after elution.
In the extraction process, the upper layer of extraction liquid is taken to obtain an extraction compound.
Preferably, the amine species comprises a primary amine.
Preferably, the primary amine includes any one of dodecylamine, hexadecylamine, or octadecylamine, or a mixture of at least two thereof, which illustratively includes a mixture of dodecylamine and hexadecylamine, a mixture of hexadecylamine and octadecylamine, or a mixture of dodecylamine and octadecylamine, and the like.
Preferably, the cyanamide species comprises melamine and/or dicyandiamide.
Preferably, the solvent for elution comprises acetone.
Preferably, the pH of the vanadyl solution is 1-6, such as 1, 1.5, 2, 3, 4, 5, or 6, etc., preferably 1.5-3.
The invention controls the pH value of the vanadyl acid solution to be 1-6, which is beneficial to the combination of the amine extractant and V, thereby improving the yield of the preparation process and further improving the content of vanadium nitride in the product.
Preferably, the preparation method of the vanadyl solution comprises the step of adding acid into the vanadium-containing solution to adjust the pH value to obtain the vanadyl solution.
Preferably, the acid used to adjust the pH comprises sulfuric acid.
Preferably, the vanadium-containing solution is selected from any one of or a mixture of at least two of a vanadium salt dissolved in water, vanadium-containing industrial wastewater or leaching solution of vanadium-chromium waste residue.
The method adopts an extraction process to reduce the requirement of the preparation process on the purity of vanadium species in the vanadyl acid solution, thereby reducing the cost of the preparation process, and meanwhile, the method is suitable for recycling metal ions in vanadium-containing industrial wastewater and vanadium-chromium waste residue leachate, and realizes the resource utilization of waste.
Preferably, the concentration of vanadium element in the vanadium-containing solution is 0.06-0.24mol/L, such as 0.06mol/L, 0.12mol/L, 0.18mol/L or 0.24mol/L, etc., preferably 0.12 mol/L.
Preferably, the vanadium salt comprises sodium metavanadate.
Preferably, the molar ratio of the amine substance in the step (1) to the vanadium element in the vanadyl solution is (0.5-5):1, such as 0.5:1, 1:1, 2:1, 3:1, 4:1 or 5:1, and preferably (1-2): 1.
Preferably, the molar ratio of the cyanamide-based substance to the vanadium element in the vanadyl solution is (5-10):1, such as 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, and preferably (6-7): 1.
Preferably, the non-reducing atmosphere in step (2) comprises any one or a combination of at least two of nitrogen, ammonia, or argon, and the mixture exemplarily comprises a mixture of nitrogen and ammonia, a mixture of nitrogen and argon, or a mixture of ammonia and argon, and the like.
Preferably, the calcination process is divided into a first stage calcination and a second stage calcination in sequence.
Preferably, the temperature of the first stage calcination is 450-650 deg.C, such as 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C or 650 deg.C, etc.
Preferably, the temperature rise rate of the first stage calcination is 1-5 deg.C/min, such as 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, or 5 deg.C/min, etc., preferably 2 deg.C/min.
Preferably, the first stage calcination is carried out for a period of 1 to 8 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, etc., preferably 4 hours.
Preferably, the temperature of the second stage calcination is 700-1200 ℃, such as 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃ or 1200 ℃, and the like, preferably 800 ℃.
Preferably, the temperature rise rate of the second stage calcination is 1-5 deg.C/min, such as 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, or 5 deg.C/min, etc., preferably 2 deg.C/min.
Preferably, the time of the second stage calcination is 1 to 8h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc., preferably 2 h.
As a preferred technical scheme of the invention, the method comprises the following steps:
(a) adding sulfuric acid into the vanadium-containing solution to adjust the pH value to 1-6 to obtain vanadyl acid solution; the vanadium-containing solution is selected from any one or a mixture of at least two of vanadium salt dissolved in water, vanadium-containing industrial wastewater or leaching solution of vanadium-chromium waste residue; the concentration of vanadium element in the vanadium-containing solution is 0.06-0.24 mol/L;
(b) mixing a mixture of primary amine and cyanamide substances with an organic solvent with a vanadyl acid solution to obtain an extract compound; the molar ratio of the primary amine to the vanadium element in the vanadyl solution is (0.5-5) to 1; the molar ratio of the cyanamide substance to the vanadium element in the vanadyl acid solution is (5-10) to 1;
(c) calcining the dried extract compound in the step (b) in a non-oxidizing atmosphere to obtain the vanadium nitride-pore carbon nanocomposite; the non-oxidizing atmosphere comprises any one or a combination of at least two of nitrogen, ammonia or argon; the calcination process is divided into a first section of calcination and a second section of calcination in sequence; the temperature of the first-stage calcination is 450-650 ℃; the temperature rise rate of the first-stage calcination is 1-5 ℃/min, the time of the first-stage calcination is 1-8h, the temperature of the second-stage calcination is 700-1200 ℃, the temperature rise rate of the second-stage calcination is 1-5 ℃/min, and the time of the second-stage calcination is 1-8 h.
In a second aspect, the present invention provides a vanadium nitride-porous carbon nanocomposite material prepared by the method according to the first aspect, wherein the vanadium nitride has an average particle size of 2-10nm, such as 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, or 10 nm.
In a third aspect, the present invention provides the use of a vanadium nitride-porous carbon nanocomposite material according to the second aspect as an energy storage material.
Preferably, the composite material is used for preparing a supercapacitor or a lithium ion battery.
In a fourth aspect, the invention provides a method for recovering metal ions in vanadium-containing industrial wastewater or vanadium-chromium waste residue leachate, which comprises the following steps:
(1) mixing a mixture of an amine substance, a cyanamide substance and an organic solvent with a vanadyl acid solution to obtain an extract compound; the preparation method of the vanadyl acid solution comprises the steps of adding acid into the vanadyl acid solution to adjust the pH value to obtain the vanadyl acid solution; the vanadium-containing solution is selected from vanadium-containing industrial wastewater and/or vanadium-chromium waste residue leachate;
(2) and (2) calcining the dried extract compound in the step (1) in a non-oxidizing atmosphere to obtain the vanadium nitride-pore carbon nanocomposite.
When the vanadium-containing industrial wastewater or the vanadium-chromium waste residue leaching solution is used as a raw material in the preparation process, the vanadium is enriched through the extraction process, the resource utilization of metal ions in the vanadium-containing industrial wastewater or the vanadium-chromium waste residue leaching solution is realized, and the method has a wide application prospect.
Preferably, the method for obtaining the extract compound in the step (1) comprises the step of standing the mixed solution or separating the mixed solution after elution.
Preferably, the amine species comprises a primary amine.
Preferably, the primary amine comprises any one of or a mixture of at least two of dodecylamine, octadecylamine or hexadecylamine, which mixture exemplarily comprises a mixture of dodecylamine and octadecylamine, a mixture of hexadecylamine and octadecylamine, or the like.
Preferably, the cyanamide species comprises melamine and/or dicyandiamide.
Preferably, the solvent for elution comprises acetone.
Preferably, the pH of the vanadyl solution is 1-6, such as 1, 1.5, 2, 3, 4, 5, or 6, etc., preferably 1.5-3.
Preferably, the concentration of the vanadium element in the vanadium-containing solution is 0.06-0.24mol/L, 0.06mol/L, 0.12mol/L, 0.18mol/L or 0.24mol/L, etc., preferably 0.12 mol/L.
Preferably, the acid used to adjust the pH comprises sulfuric acid.
Preferably, the molar ratio of the amine substance in the step (1) to the vanadium element in the vanadyl solution is (0.5-5):1, such as 0.5:1, 1:1, 2:1, 3:1, 4:1 or 5:1, and preferably (1-2): 1.
Preferably, the molar ratio of the cyanamide-based substance to the vanadium element in the vanadyl solution is (5-10):1, such as 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, and preferably (6-7): 1.
Preferably, the non-oxidizing atmosphere of step (2) comprises any one or a combination of at least two of nitrogen, ammonia, or argon.
Preferably, the calcination process is divided into a first stage calcination and a second stage calcination in sequence.
Preferably, the temperature of the first stage calcination is 450-650 deg.C, such as 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C or 650 deg.C, etc.
Preferably, the temperature rise rate of the first stage calcination is 1-5 deg.C/min, such as 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, or 5 deg.C/min, etc., preferably 2 deg.C/min.
Preferably, the first stage calcination is carried out for a period of 1 to 8 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, etc., preferably 4 hours.
Preferably, the temperature of the second stage calcination is 700-1200 ℃, such as 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃ or 1200 ℃, preferably 800 ℃.
Preferably, the temperature rise rate of the second stage calcination is 1-5 deg.C/min, such as 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, or 5 deg.C/min, etc., preferably 2 deg.C/min.
Preferably, the time of the second stage calcination is 1 to 8h, such as 1h, 2h, 3h or 4h, etc., preferably 2 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the vanadium nitride-porous carbon nanocomposite, vanadium in the vanadyl acid solution is extracted into the extraction compound by an extraction method, the extraction compound is dried and then calcined in a non-oxidizing atmosphere to obtain the vanadium nitride-porous carbon nanocomposite, the preparation process adopts an extraction mode, so that the purity requirement on vanadium species in the vanadyl acid solution in the preparation process is low, and the amine extractant is used as a carbon source and a nitrogen source in the preparation process, so that the cost of the preparation process is reduced;
(2) the average grain diameter of vanadium nitride in the vanadium nitride-pore carbon nano composite material prepared by the method is 2-10nm, and the content of vanadium nitride in V species can reach 42.5 percent to the maximum;
(3) the method can be used for recovering vanadium in vanadium-containing industrial wastewater and vanadium-chromium waste residue leachate.
Drawings
FIG. 1 is a scanning electron microscope image of a vanadium nitride-porous carbon nanocomposite prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the vanadium nitride-porous carbon nanocomposite prepared in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of the vanadium nitride-porous carbon nanocomposite prepared in example 1 of the present invention;
FIG. 4 is a transmission electron microscope image of the vanadium nitride-porous carbon nanocomposite prepared in example 1 of the present invention;
FIG. 5 is an X-ray powder diffraction pattern of vanadium nitride-porous carbon nanocomposites prepared in examples 1-3 of the present invention;
FIG. 6 is a Raman spectrum of a vanadium nitride-channel carbon nanocomposite prepared according to examples 1 to 3 of the present invention;
FIG. 7 is a CV curve diagram of test in 6M potassium hydroxide electrolyte under a three-electrode system condition after the vanadium nitride-porous carbon nanocomposite prepared in example 1 of the present invention is prepared into an electrode, with sweep rates of 10mV/s and 50mV/s, and a voltage range of-1V to 0.2V.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the vanadium nitride-pore carbon nano composite material comprises the following steps:
(a) adding 5M sulfuric acid into 100mL vanadium-containing solution to adjust the pH value to 1.5 to obtain vanadyl acid solution; the vanadium-containing solution is selected from sodium metavanadate aqueous solution, and the concentration of vanadium element in the vanadium-containing solution is 0.12 mol/L;
(b) dissolving 2.24g of dodecylamine and 10g of melamine in 100mL of n-hexane solution, then adding the vanadyl acid radical solution obtained in the step (a), mixing for 30min, standing for 30min, and separating to obtain an extract compound;
(c) after vacuum drying at 60 ℃, calcining the extract compound in a non-oxidizing atmosphere to obtain the vanadium nitride-pore carbon nanocomposite; the non-oxidizing atmosphere is nitrogen, and the calcining process is divided into a first section of calcining and a second section of calcining in sequence; the temperature of the first stage calcination is 600 ℃; the temperature rise rate of the first-stage calcination is 2 ℃/min, the time of the first-stage calcination is 4h, the temperature of the second-stage calcination is 800 ℃, the temperature rise rate of the second-stage calcination is 2 ℃/min, and the time of the second-stage calcination is 2 h.
Scanning electron micrographs of the vanadium nitride-porous carbon nanocomposite prepared in this example are shown in fig. 1 and fig. 2; the transmission electron microscope images are shown in FIG. 3 and FIG. 4; it can be seen from the combination of fig. 1-4 that vanadium nitride is uniformly distributed on the channel carbon, and the average particle diameter of vanadium nitride is 2.4nm, and from fig. 4, the lattice diagram of vanadium nitride can also be seen, the lattice spacing of which is 0.206nm, which is the (200) crystal plane of VN.
Example 2
In the embodiment, the vanadium-containing solution in the embodiment 1 is replaced by ammonium metavanadate solution with the concentration of 0.06mol/L in an equal volume; adjusting the pH value to 3; other conditions were exactly the same as in example 1.
Example 3
This example replaces the pH of step (1) in example 1 with 2 and the temperature of the first stage calcination with 500 ℃, all other conditions being exactly the same as in example 1.
The X-ray powder diffraction pattern of the vanadium nitride-porous carbon nanocomposite prepared in examples 1-3 is shown in FIG. 5, from which it can be seen that the product is composed of vanadium nitride (JCPDS card number PDF #73-2038) and carbon.
The raman spectra of the vanadium nitride-channel carbon nanocomposites prepared in examples 1-3 are shown in fig. 6, which shows that the channel carbon comprises graphitic carbon and amorphous carbon.
After the vanadium nitride-porous carbon nanocomposite prepared in example 1 is prepared into an electrode, CV curves tested in 6M potassium hydroxide electrolyte under a three-electrode system condition are shown in FIG. 7, sweep rates are 10mV/s and 50mV/s, and a voltage range is-1-0.2V; as can be seen, the specific capacitance obtained for the electrode at 50mV/s was 285F/g.
Example 4
This example replaces the pH of step (1) in example 1 with 3, and the other conditions are exactly the same as in example 1.
Example 5
This example replaces the pH of step (1) in example 1 with 1, and the other conditions are exactly the same as in example 1.
Example 6
This example replaces the pH of step (1) in example 1 with 6, and the other conditions are exactly the same as in example 1.
Example 7
This example replaces the amount of dodecylamine added in example 1 with 4.48g, otherwise exactly the same conditions are used as compared to example 1.
Example 8
This example replaces the amount of dodecylamine added in example 1 with 11.2g, and the other conditions are exactly the same as in example 1.
Example 9
This example replaces the amount of dodecylamine added in example 1 with 1.12g, and the other conditions are exactly the same as in example 1.
Example 10
This example replaces 12g of dodecylamine added in example 1 with the same other conditions as in example 1.
Example 11
This example replaces the amount of dodecylamine added in example 1 with 0.5g, and the other conditions are exactly the same as in example 1.
Example 12
In the embodiment, the vanadium-containing solution in the embodiment 1 with the same volume is replaced by the simulated vanadium-chromium waste residue leaching solution, and the vanadium and chromium concentrations in the leaching solution are the same and are all 0.24 mol/L; in the extraction process, after the vanadium and the chromium are separated by adopting N1923, the vanadium is enriched into an organic phase, then 20ml of acetone is added into the organic phase for elution, 10g of melamine is added into the eluted organic phase, the mixture is fully mixed and then is kept stand for liquid separation, and other conditions are completely the same as those in the embodiment 1.
Example 13
This example replaces the dodecylamine in example 1 with N-methyldodecylamine, otherwise exactly the same as in example 1.
Comparative example 1
This comparative example differs from example 1 in that the pH was not adjusted in step (1) and the other conditions were exactly the same as in example 1.
Comparative example 2
This comparative example replaces the pH of step (1) in example 1 with 7, and the other conditions are exactly the same as in example 1.
Comparative example 3
This comparative example replaces the pH of step (1) in example 1 with 0.5, and the other conditions are exactly the same as in example 1.
And (3) performance testing:
the average particle size of vanadium nitride in the vanadium nitride-porous carbon nanocomposites prepared in examples 1-13 and comparative examples 1-3 was analyzed by transmission electron microscopy and the average particle size obtained from the test is shown in table 1:
the contents of V-N in the V species in the vanadium nitride-porous carbon nanocomposites prepared in examples 1-13 and comparative examples 1-3 were measured by XPS, and the results are shown in table 1:
TABLE 1
Figure BDA0001986057450000131
Figure BDA0001986057450000141
As can be seen from the table above, in comparative example 1 and comparative examples 1 to 3, when the pH of the vanadyl solution is controlled to be 1 to 6, the average particle size of vanadium nitride in the vanadium nitride-porous carbon nanocomposite prepared by the method is 2 to 10nm, and the content of V-N in V species can reach 42.5 percent at most; comparing example 1 with examples 4-6, it can be seen that the vanadium nitride-porous carbon nanocomposite prepared by the method has a higher content of vanadium nitride when the pH of the vanadyl acid solution is 1.5-3.
Comparing example 1 with examples 7-11, it can be seen that when the molar ratio of the primary amine to the vanadium element in the vanadyl solution is controlled to (0.5-5):1, the average particle size of the vanadium nitride in the product prepared therefrom is small, and the vanadium species in the product thereof has a high content of V-N, and the optimum molar ratio of the primary amine to the vanadium element in the vanadyl solution is (1-2): 1.
From example 12, it can be seen that the vanadium nitride-porous carbon nanocomposite material of the present invention can be prepared by using the simulated vanadium-chromium waste residue leachate as a raw material, thereby achieving recovery and resource utilization of vanadium in the vanadium-chromium waste residue leachate.
It can be seen from comparing examples 1 and 13 that primary amines are more effective as extractants than secondary amines.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A preparation method of a vanadium nitride-pore carbon nano composite material is characterized by comprising the following steps:
(1) mixing a mixture of an amine substance, a cyanamide substance and an organic solvent with a vanadyl acid solution to obtain an extract compound;
(2) and (2) calcining the dried extract compound in the step (1) in a non-oxidizing atmosphere to obtain the vanadium nitride-pore carbon nanocomposite.
2. The method of claim 1, wherein the method for obtaining the extract compound in step (1) comprises standing the mixed solution or separating the solution after elution;
preferably, the amine species comprises a primary amine;
preferably, the primary amine comprises any one or a mixture of at least two of dodecylamine, hexadecylamine or octadecylamine;
preferably, the cyanamide species comprises melamine and/or dicyandiamide;
preferably, the solvent for elution comprises acetone.
3. The method according to claim 1 or 2, wherein the vanadyl solution has a pH of 1-6, preferably 1.5-3;
preferably, the preparation method of the vanadyl solution comprises the steps of adding acid into the vanadium-containing solution to adjust the pH value to obtain the vanadyl solution;
preferably, the acid used to adjust the pH comprises sulfuric acid;
preferably, the vanadium-containing solution is selected from any one of or a mixture of at least two of a vanadium salt dissolved in water, vanadium-containing industrial wastewater or leaching solution of vanadium-chromium waste residue;
preferably, the concentration of the vanadium element in the vanadium-containing solution is 0.06-0.24mol/L, preferably 0.12 mol/L;
preferably, the vanadium salt comprises sodium metavanadate.
4. The method according to any one of claims 1 to 3, wherein the molar ratio of the amine-type substance to the vanadium element in the vanadyl solution in step (1) is (0.5-5):1, preferably (1-2): 1;
preferably, the molar ratio of the cyanamide substance to the vanadium element in the vanadyl solution is (5-10):1, preferably (6-7): 1.
5. The method of any one of claims 1 to 4, wherein the non-oxidizing atmosphere of step (2) comprises any one or a combination of at least two of nitrogen, ammonia, or argon;
preferably, the calcination process in the step (2) is divided into a first stage calcination and a second stage calcination in sequence;
preferably, the temperature of the first stage calcination is 450-650 ℃;
preferably, the temperature rise rate of the first stage calcination is 1-5 ℃/min, preferably 2 ℃/min;
preferably, the first stage calcination is carried out for a period of time of 1 to 8 hours, preferably 4 hours;
preferably, the temperature of the second stage calcination is 700-1200 ℃, preferably 800 ℃;
preferably, the temperature rise rate of the second stage calcination is 1-5 ℃/min, preferably 2 ℃/min;
preferably, the time of the second stage calcination is 1 to 8 hours, preferably 2 hours.
6. The method according to any one of claims 1 to 5, characterized in that it comprises the steps of:
(a) adding sulfuric acid into the vanadium-containing solution to adjust the pH value to 1-6 to obtain vanadyl acid solution; the vanadium-containing solution is selected from any one or a mixture of at least two of vanadium salt dissolved in water, vanadium-containing industrial wastewater or leaching solution of vanadium-chromium waste residue, and the concentration of vanadium element in the vanadium-containing solution is 0.06-0.24 mol/L;
(b) mixing a mixture of primary amine and cyanamide substances with an organic solvent with a vanadyl acid solution to obtain an extract compound; the molar ratio of the primary amine to the vanadium element in the vanadyl solution is (0.5-5) to 1; the molar ratio of the cyanamide substance to the vanadium element in the vanadyl acid solution is (5-10) to 1;
(c) calcining the dried extract compound in the step (b) in a non-reducing atmosphere to obtain the vanadium nitride-pore carbon nanocomposite; the non-oxidizing atmosphere comprises any one or a combination of at least two of nitrogen, ammonia or argon; the calcination process is divided into a first section of calcination and a second section of calcination in sequence; the temperature of the first-stage calcination is 450-650 ℃; the temperature rise rate of the first-stage calcination is 1-5 ℃/min, the time of the first-stage calcination is 1-8h, the temperature of the second-stage calcination is 700-1200 ℃, the temperature rise rate of the second-stage calcination is 1-5 ℃/min, and the time of the second-stage calcination is 1-8 h.
7. The vanadium nitride-porous carbon nanocomposite prepared according to any one of claims 1 to 6, wherein the vanadium nitride has an average particle size of 2 to 10 nm.
8. Use of the vanadium nitride-porous carbon nanocomposite according to claim 7 as an energy storage material;
preferably, the composite material is used for preparing a supercapacitor or a lithium ion battery.
9. A method for recovering metal ions in vanadium-containing industrial wastewater or vanadium-chromium waste residue leachate is characterized by comprising the following steps:
(1) mixing a mixture of an amine substance, a cyanamide substance and an organic solvent with a vanadyl acid solution to obtain an extract compound; the preparation method of the vanadyl acid solution comprises the steps of adding acid into the vanadyl acid solution to adjust the pH value to obtain the vanadyl acid solution; the vanadium-containing solution is selected from vanadium-containing industrial wastewater and/or vanadium-chromium waste residue leachate;
(2) and (2) calcining the dried extract compound in the step (1) in a non-oxidizing atmosphere to obtain the vanadium nitride-pore carbon nanocomposite.
10. The method of claim 9, wherein the method for obtaining the extract compound in step (1) comprises standing the mixed solution or separating the solution after elution;
preferably, the amine species comprises a primary amine;
preferably, the primary amine comprises any one or a mixture of at least two of dodecylamine, hexadecylamine or octadecylamine;
preferably, the cyanamide species comprises melamine and/or dicyandiamide;
preferably, the solvent for elution comprises acetone;
preferably, the pH of the vanadyl solution is 1-6, preferably 1.5-3;
preferably, the concentration of the vanadium element in the vanadium-containing solution is 0.06-0.24mol/L, preferably 0.12 mol/L;
preferably, the acid used to adjust the pH comprises sulfuric acid;
preferably, the molar ratio of the amine substance to the vanadium element in the vanadyl solution is (0.5-5) to 1, preferably (1-2) to 1;
preferably, the molar ratio of the cyanamide substance to the vanadium element in the vanadyl solution is (5-10):1, preferably (6-7): 1;
preferably, the non-oxidizing atmosphere of step (2) comprises any one or a combination of at least two of nitrogen, ammonia, or argon;
preferably, the calcination process is divided into a first stage calcination and a second stage calcination in sequence;
preferably, the temperature of the first stage calcination is 450-650 ℃;
preferably, the temperature rise rate of the first stage calcination is 1-5 ℃/min, preferably 2 ℃/min;
preferably, the first stage calcination is carried out for a period of time of 1 to 8 hours, preferably 4 hours;
preferably, the temperature of the second stage calcination is 700-1200 ℃, preferably 800 ℃;
preferably, the temperature rise rate of the second stage calcination is 1-5 ℃/min, preferably 2 ℃/min;
preferably, the time of the second stage calcination is 1 to 8 hours, preferably 2 hours.
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CN101717076A (en) * 2009-11-27 2010-06-02 华南师范大学 Method for preparing vanadium nitride
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