CN108624992B - Spiral nano carbon fiber and preparation method thereof - Google Patents
Spiral nano carbon fiber and preparation method thereof Download PDFInfo
- Publication number
- CN108624992B CN108624992B CN201810589099.1A CN201810589099A CN108624992B CN 108624992 B CN108624992 B CN 108624992B CN 201810589099 A CN201810589099 A CN 201810589099A CN 108624992 B CN108624992 B CN 108624992B
- Authority
- CN
- China
- Prior art keywords
- solution
- spiral
- preparing
- plating solution
- carbon black
- 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.)
- Active
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1273—Alkenes, alkynes
- D01F9/1275—Acetylene
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a spiral carbon nanofiber and a preparation method thereof, and belongs to the technical field of carbon fiber preparation. According to the invention, the modified carbon black is added into the plating solution for preparing the nickel-phosphorus coating, and carbon black particles modified by oxidation of concentrated nitric acid are beneficial to forming more uniform nano gaps on the nickel-phosphorus coating in the etching stage, so that the catalytic activity is improved, a favorable growth environment is further provided for the growth of subsequent spiral carbon nanofibers, and the macroscopic growth of the spiral carbon nanofibers is realized. The invention adopts the anodic oxidation etching method to etch the nickel-phosphorus coating, has stronger controllability, and can strictly control the process parameters such as the concentration of electrolyte, voltage or current, time and the like, thereby effectively avoiding the problem that the reaction rate is not easy to control caused by adopting chemical etching in the prior art and realizing the controllable process preparation of the nano porous nickel-phosphorus material. The spiral carbon nanofiber prepared by the method has the advantages of good appearance, high yield, simple process and high repeatability.
Description
Technical Field
The invention relates to the technical field of carbon fiber preparation, in particular to a spiral carbon nanofiber and a preparation method thereof.
Background
The spiral carbon nanofiber is a material with very excellent performance, has excellent physical and chemical properties such as high specific surface area, high specific modulus, high conductivity, low density, high elasticity and the like due to the special spiral shape, and is expected to have new potential applications in many fields, such as high-performance electromagnetic wave absorption devices, high-specific-capacity batteries, touch sensors, nano electromechanical equipment, hydrogen storage devices and the like.
At present, Chemical Vapor Deposition (CVD) is mainly used for preparing the spiral carbon nanofibers at home and abroad, graphite or ceramic is used as a matrix, then catalyst particles are paved on the matrix, hydrocarbon gas is introduced at high temperature for catalytic pyrolysis, and the spiral carbon nanofibers are separated out on the catalyst particles. The spiral carbon nanofibers with high purity can be prepared by the method, but the method is often greatly influenced by catalyst particles, and the grown spiral carbon nanofibers are generally low in yield, complex in process and high in cost.
Disclosure of Invention
The invention aims to provide a spiral carbon nanofiber and a preparation method thereof, and solves the problems that the existing preparation method is complex in process, high in cost, low in yield and incapable of realizing mass production.
The technical scheme for solving the technical problems is as follows:
a method for preparing a spiral carbon nanofiber, comprising:
(1) preparing a nano porous nickel-phosphorus material:
(11) placing the carbon black in concentrated nitric acid, heating in an oil bath at the temperature of 80-100 ℃, condensing, refluxing, and stirring for reaction for 15-20 hours to obtain modified carbon black; mixing lactic acid, nickel sulfate and citric acid to prepare a first solution, and mixing sodium hypophosphite and sodium acetate to prepare a second solution; mixing the first solution and the second solution to a constant volume, adding modified carbon black, performing ultrasonic oscillation for 20-30 min, and adjusting the pH value to 4-5 to prepare a plating solution;
wherein the mass ratio of the lactic acid to the nickel sulfate to the citric acid to the sodium hypophosphite to the sodium acetate to the modified carbon black is as follows: (36-48): (30-45): (2-8): (20-35): (15-25): (0.01 to 0.1);
(12) placing the purified substrate sample in the plating solution obtained in the step (11), stirring the plating solution, plating for 2-3h at the temperature of 70-85 ℃, cleaning and drying;
(13) taking a phosphoric acid solution with the concentration of 1-5 mol/L as an electrolyte, etching the substrate sample obtained in the step (12) for 30-50 min at the temperature of 20-25 ℃ and the voltage of 0.5-1V, cleaning and drying to obtain the nano porous nickel-phosphorus material;
(2) and (3) raising the nano porous nickel-phosphorus material to 500-700 ℃ at the speed of 2-8 ℃/min in an inert atmosphere, preserving the heat for 8-15 min, and then introducing acetylene to react for 20-60 min to obtain the spiral carbon nanofiber.
The invention prepares the nano porous nickel-phosphorus material beneficial to the growth of the spiral carbon nanofibers by designing process steps, adjusting process parameters and proportioning raw materials, thereby realizing the macro growth of the spiral carbon nanofibers. Specifically, the method comprises the following steps:
firstly, the modified carbon black is added into the plating solution for preparing the nickel-phosphorus coating, and carbon black particles modified by oxidation of concentrated nitric acid are beneficial to forming more uniform nanometer gaps on the nickel-phosphorus coating in the etching stage, so that the catalytic activity is improved, and a favorable growth environment is provided for the growth of subsequent spiral carbon nanofibers. The nano carbon black particles subjected to nitric acid oxidation modification treatment can obviously improve the dispersibility of the carbon black particles in the plating solution and the stability of the plating solution, so that the nano pore structure on the surface of the carbon black is smaller and more uniform, has a higher specific surface area, exerts higher catalytic performance and realizes the macro growth of the spiral nano carbon fiber.
And the prepared nickel-phosphorus coating is etched by adopting an anodic oxidation etching method, so that the controllability is stronger, and the process parameters such as electrolyte concentration, voltage or current, time and the like can be strictly controlled, so that the problem that the reaction rate is difficult to control in the prior art due to chemical etching is effectively solved, and the controllable process preparation of the nano porous nickel-phosphorus material is realized. In addition, the first solution and the second solution are respectively prepared when the plating solution is prepared, and the nickel sulfate used as the oxidant and the sodium hypophosphite used as the reducing agent are separately prepared, so that the reaction is prevented from being carried out in advance in the preparation process, the further control of the reaction is realized, and the controllability of the preparation process is improved.
Further, in the step (12), the pH value of the plating solution is adjusted every 10-30 min.
The invention can overcome the defect of pH reduction caused by reaction by continuously adjusting the pH value of the plating solution, thereby ensuring the stability of the plating solution.
Further, in the step (12), the plating solution is stirred at a rotating speed of 100-140 r/min during plating, and the mouth of the container filled with the plating solution is sealed.
The reaction is more fully performed by stirring; the evaporation of the plating solution in the reaction process can be reduced by sealing the opening of the container.
Further, in the step (12), the step of purifying the substrate sample includes:
s1: grinding and polishing the cut substrate sample;
s2: placing a substrate sample in an alkaline degreasing liquid, soaking for 10-20 min at 60-90 ℃, and then cleaning;
s3: and (3) placing the substrate sample into an acid rust removing solution, soaking for 3-7 min at the temperature of 20-40 ℃, and then cleaning.
The surface of the base material sample is smoother to facilitate smooth reaction and formation of a coating through grinding and polishing, and meanwhile, the base material sample after grinding and polishing is cleaned by the alkaline degreasing liquid to obtain a bright, flat and compact nickel-phosphorus-carbon alloy coating so as to further assist smooth reaction. In addition, because the base material sample is generally steel and is easy to be oxidized in the air, the invention can further clean the sample by the acid rust removing solution, not only remove rust, but also activate the surface of the sample, and is beneficial to the smooth proceeding of chemical plating reaction.
Further, the alkaline degreasing fluid comprises the following components in percentage by mass (3.5-4.5) to (3-5): (3.5-4.5) sodium hydroxide, sodium carbonate and sodium phosphate.
Further, the acidic derusting liquid is a hydrochloric acid solution with the volume concentration of 5-20%.
Furthermore, the aeration rate of the inert atmosphere is 80-100 sccm, and the inert atmosphere is nitrogen.
Further, the aeration rate of acetylene is 60 to 100 sccm.
The spiral carbon nanofiber prepared by the method is provided.
The invention has the following beneficial effects:
the invention gives full play to the activity of the nano porous nickel-phosphorus material, realizes the macro growth of the spiral carbon nanofiber, and the grown spiral carbon nanofiber has good appearance, high yield, simple process, good controllability and high repeatability.
According to the invention, carbon black particles modified by nitric acid oxidation are introduced into the nickel-phosphorus coating, so that the dispersibility of the carbon black particles is better, and the prepared nano-porous nickel material has a unique uniform nano-pore structure and stronger catalytic activity. The invention uses the etched nano-porous nickel-phosphorus material as a catalyst, and compared with the Ni-P-C alloy which is not etched, the spiral nano-carbon fiber can be grown in a macroscopic quantity.
Drawings
FIG. 1 is a photograph showing the growth of the spiral filamentous nanocarbon prepared in example 3;
FIG. 2 is a SEM image of example 3;
FIG. 3 is a photograph showing the growth of the spiral filamentous nanocarbon prepared in comparative example 1;
FIG. 4 is a photograph showing the growth of the spiral filamentous nanocarbon prepared in comparative example 2;
FIG. 5 is a photograph showing the growth of the spiral filamentous nanocarbon prepared in comparative example 3;
fig. 6 is a photograph showing the growth of the spiral filamentous nanocarbon prepared in comparative example 4.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
the preparation method of the spiral carbon nanofiber comprises the following steps:
1. preparing a nano porous nickel-phosphorus material:
(11) preparing a plating solution:
(1.1) preparation of modified carbon Black: placing the carbon black in concentrated nitric acid, heating in an oil bath at the temperature of 80 ℃, condensing, refluxing, and stirring for reacting for 20 hours to obtain the modified carbon black. Cooling to room temperature, centrifugally washing to neutrality and drying for later use.
(1.2) preparing a first solution: lactic acid, nickel sulfate and citric acid are compounded to form a first solution. Specifically, lactic acid is taken in a beaker, 100ml of distilled water is added for full mixing, nickel sulfate is weighed in the beaker, citric acid is added, and a glass rod is used for continuously stirring until the nickel sulfate is completely dissolved to form a uniform transparent solution, so that a first solution is prepared.
(1.3) preparing a second solution: mixing sodium hypophosphite and sodium acetate to prepare a second solution. Specifically, the method comprises the following steps: weighing sodium hypophosphite in another beaker, adding 100ml of distilled water to fully dissolve the sodium hypophosphite, taking sodium acetate in the beaker, and stirring with a glass rod in the same way until a stable and uniform solution is formed to prepare a second solution.
(1.4) mixing the first solution and the second solution to a constant volume of 250ml, adding modified carbon black, carrying out ultrasonic oscillation for 20min, and adjusting the pH value to 4 to obtain the plating solution.
Wherein the mass ratio of the lactic acid to the nickel sulfate to the citric acid to the sodium hypophosphite to the sodium acetate to the modified carbon black is as follows: 36: 32.8: 3: 23.2: 16.4: 0.02;
(12) and (3) placing the purified substrate sample in the plating solution in the step (11), stirring the plating solution at the rotating speed of 100r/min, sealing the opening of a container filled with the plating solution, and adjusting the pH of the plating solution every 10min to keep the pH at 4. Plating at 70 deg.C for 3 hr, cleaning, and drying.
The step of cleaning the substrate sample comprises:
s1: grinding and polishing the cut substrate sample; the sample was cut into a size of 10 mm. times.10 mm. times.3 mm. The surface and the section of the sample are roughly ground on a polishing machine until the surface and the section of the sample tend to be smooth. And performing fine sanding on the sand paper until the plane has mirror gloss and has less scratches (the sanding sequence is 200# → 400# → 600# → 800# → 1000# → 1200# → 1400# → 1600# → 2000 #).
S2: placing a substrate sample in a mass ratio of 3.5: 3: 3.5, soaking the 100ml alkaline deoiling liquid prepared by sodium hydroxide, sodium carbonate and sodium phosphate at the temperature of 60 ℃ for 20min, and then cleaning;
s3: the substrate sample is placed in a hydrochloric acid solution with the volume concentration of 5% to be soaked for 3min at the temperature of 40 ℃, and then is washed.
(13) And (3) taking a phosphoric acid solution with the concentration of 1mol/L as an electrolyte, etching the base material sample obtained in the step (12) for 50min at the temperature of 20 ℃ and the voltage of 0.5V, cleaning and drying to obtain the nano porous nickel-phosphorus material.
2. And (3) catalytic reaction:
placing the nano porous nickel-phosphorus material prepared by the method in a constant temperature area of a tube furnace, firstly evacuating a quartz tube by using inert gas, then heating to 500 ℃ at the speed of 2 ℃/min in the inert atmosphere of 80sccm, preserving heat for 15min, and closing the inert gas. The inert gas is preferably nitrogen, and may be helium, neon, argon, or the like. Acetylene of 60sccm was introduced and reacted for 60 min. And after the reaction is finished, cooling to room temperature in a nitrogen atmosphere to obtain the spiral carbon nanofiber.
Example 2:
the preparation method of the spiral carbon nanofiber comprises the following steps:
1. preparing a nano porous nickel-phosphorus material:
(11) preparing a plating solution:
(1.1) preparation of modified carbon Black: placing the carbon black in concentrated nitric acid, heating in an oil bath at 100 ℃, condensing, refluxing, stirring and reacting for 15 hours to obtain the modified carbon black. Cooling to room temperature, centrifugally washing to neutrality and drying for later use.
(1.2) preparing a first solution: lactic acid, nickel sulfate and citric acid are compounded to form a first solution. Specifically, lactic acid is taken in a beaker, 100ml of distilled water is added for full mixing, nickel sulfate is weighed in the beaker, citric acid is added, and a glass rod is used for continuously stirring until the nickel sulfate is completely dissolved to form a uniform transparent solution, so that a first solution is prepared.
(1.3) preparing a second solution: mixing sodium hypophosphite and sodium acetate to prepare a second solution. Specifically, the method comprises the following steps: weighing sodium hypophosphite in another beaker, adding 100ml of distilled water to fully dissolve the sodium hypophosphite, taking sodium acetate in the beaker, and stirring with a glass rod in the same way until a stable and uniform solution is formed to prepare a second solution.
(1.4) mixing the first solution and the second solution to a constant volume of 250ml, adding modified carbon black, carrying out ultrasonic oscillation for 30min, and adjusting the pH value to 5 to obtain the plating solution.
Wherein the mass ratio of the lactic acid to the nickel sulfate to the citric acid to the sodium hypophosphite to the sodium acetate to the modified carbon black is as follows: 45: 42: 7.5: 32: 22: 0.08;
(12) and (3) placing the purified substrate sample in the plating solution in the step (11), stirring the plating solution at the rotating speed of 140r/min, sealing the opening of a container filled with the plating solution, and adjusting the pH of the plating solution every 30min to keep the pH at 5. Plating at 85 deg.C for 2 hr, cleaning, and drying.
The step of cleaning the substrate sample comprises:
s1: grinding and polishing the cut substrate sample;
s2: placing a substrate sample in a mass ratio of 4.5: 5: 4.5, soaking the 100ml alkaline deoiling liquid prepared by sodium hydroxide, sodium carbonate and sodium phosphate at 90 ℃ for 10min, and then cleaning;
s3: the substrate sample is placed in a hydrochloric acid solution with the volume concentration of 20% to be soaked for 7min at the temperature of 20 ℃, and then is washed.
(13) And (3) taking a phosphoric acid solution with the concentration of 5mol/L as an electrolyte, etching the base material sample obtained in the step (12) for 30min at the temperature of 25 ℃ and the voltage of 1V, cleaning and drying to obtain the nano porous nickel-phosphorus material.
2. And (3) catalytic reaction:
placing the nano porous nickel-phosphorus material prepared by the method in a constant temperature area of a tube furnace, firstly evacuating a quartz tube by using inert gas, then heating to 700 ℃ at the speed of 8 ℃/min in the inert atmosphere of 100sccm, preserving heat for 8min, and closing the inert gas. The inert gas is preferably nitrogen, and may be helium, neon, argon, or the like. Acetylene of 100sccm was introduced and reacted for 20 min. And after the reaction is finished, cooling to room temperature in a nitrogen atmosphere to obtain the spiral carbon nanofiber.
Example 3:
the preparation method of the spiral carbon nanofiber comprises the following steps:
1. preparing a nano porous nickel-phosphorus material:
(11) preparing a plating solution:
(1.1) preparation of modified carbon Black: placing the carbon black in concentrated nitric acid, heating in an oil bath at 90 ℃, condensing, refluxing, and stirring for reacting for 18 hours to obtain the modified carbon black. Cooling to room temperature, centrifugally washing to neutrality and drying for later use.
(1.2) preparing a first solution: lactic acid, nickel sulfate and citric acid are compounded to form a first solution. Specifically, lactic acid is taken in a beaker, 100ml of distilled water is added for full mixing, nickel sulfate is weighed in the beaker, citric acid is added, and a glass rod is used for continuously stirring until the nickel sulfate is completely dissolved to form a uniform transparent solution, so that a first solution is prepared.
(1.3) preparing a second solution: mixing sodium hypophosphite and sodium acetate to prepare a second solution. Specifically, the method comprises the following steps: weighing sodium hypophosphite in another beaker, adding 100ml of distilled water to fully dissolve the sodium hypophosphite, taking sodium acetate in the beaker, and stirring with a glass rod in the same way until a stable and uniform solution is formed to prepare a second solution.
(1.4) mixing the first solution and the second solution to a constant volume of 250ml, adding modified carbon black, carrying out ultrasonic oscillation for 25min, and adjusting the pH value to 4.5 to obtain the plating solution.
Wherein the mass ratio of the lactic acid to the nickel sulfate to the citric acid to the sodium hypophosphite to the sodium acetate to the modified carbon black is as follows: 40.8: 37: 5: 27: 18: 0.04;
(12) and (3) placing the purified substrate sample in the plating solution in the step (11), stirring the plating solution at the rotating speed of 120r/min, sealing the opening of a container filled with the plating solution, and adjusting the pH of the plating solution every 20min to keep the pH at 4.5. Plating at 79 deg.C for 2.5h, cleaning, and drying.
The step of cleaning the substrate sample comprises:
s1: grinding and polishing the cut substrate sample;
s2: placing a substrate sample in a mass ratio of 4: 3.8: 4, soaking the 100ml alkaline deoiling liquid prepared by sodium hydroxide, sodium carbonate and sodium phosphate at the temperature of 80 ℃ for 15min, and then cleaning;
s3: the substrate sample is placed in a hydrochloric acid solution with the volume concentration of 10% to be soaked for 5min at the temperature of 30 ℃, and then is washed.
(13) And (3) taking a phosphoric acid solution with the concentration of 2mol/L as an electrolyte, etching the base material sample obtained in the step (12) for 40min at the temperature of 22 ℃ and the voltage of 0.8V, cleaning and drying to obtain the nano porous nickel-phosphorus material.
2. And (3) catalytic reaction:
placing the nano porous nickel-phosphorus material prepared by the method in a constant temperature area of a tube furnace, firstly evacuating a quartz tube by using inert gas, then heating to 600 ℃ at the speed of 4 ℃/min in 90sccm inert atmosphere, preserving heat for 10min, and closing the inert gas. The inert gas is preferably nitrogen, and may be helium, neon, argon, or the like. Acetylene of 80sccm was introduced and reacted for 45 min. And after the reaction is finished, cooling to room temperature in a nitrogen atmosphere to obtain the spiral carbon nanofiber.
Comparative example 1:
this comparative example is partially the same as example 3, but the plating solution lacks carbon black and the plated substrate is not subjected to the etching reaction of step (13). The method comprises the following specific steps:
1. preparing a nano porous nickel-phosphorus material:
(11) preparing a plating solution:
(1.1) preparing a first solution: lactic acid, nickel sulfate and citric acid are compounded to form a first solution. Specifically, lactic acid is taken in a beaker, 100ml of distilled water is added for full mixing, nickel sulfate is weighed in the beaker, citric acid is added, and a glass rod is used for continuously stirring until the nickel sulfate is completely dissolved to form a uniform transparent solution, so that a first solution is prepared.
(1.2) preparing a second solution: mixing sodium hypophosphite and sodium acetate to prepare a second solution. Specifically, the method comprises the following steps: weighing sodium hypophosphite in another beaker, adding 100ml of distilled water to fully dissolve the sodium hypophosphite, taking sodium acetate in the beaker, and stirring with a glass rod in the same way until a stable and uniform solution is formed to prepare a second solution.
(1.3) mixing the first solution and the second solution to a constant volume of 250ml, and adjusting the pH value to 4.5 to prepare the plating solution.
Wherein the mass ratio of the lactic acid to the nickel sulfate to the citric acid to the sodium hypophosphite to the sodium acetate is as follows: 40.8: 37: 5: 27: 18;
(12) and (3) placing the purified substrate sample in the plating solution in the step (11), stirring the plating solution at the rotating speed of 120r/min, sealing the opening of a container filled with the plating solution, and adjusting the pH of the plating solution every 20min to keep the pH at 4.5. Plating at 79 deg.C for 2.5h, cleaning, and drying.
The procedure for the purification treatment of the substrate sample was the same as in example 3.
2. And (3) catalytic reaction:
placing the nano porous nickel-phosphorus material prepared by the method in a constant temperature area of a tube furnace, firstly evacuating a quartz tube by using inert gas, then heating to 600 ℃ at the speed of 4 ℃/min in 90sccm inert atmosphere, preserving heat for 10min, and closing the inert gas. The inert gas is preferably nitrogen, and may be helium, neon, argon, or the like. Acetylene of 80sccm was introduced and reacted for 45 min. And after the reaction is finished, cooling to room temperature in a nitrogen atmosphere to obtain the spiral carbon nanofiber.
Comparative example 2:
this comparative example is partially identical to example 3, but lacks carbon black in the bath. The method comprises the following specific steps:
1. preparing a nano porous nickel-phosphorus material:
(11) preparing a plating solution:
(1.1) preparing a first solution: lactic acid, nickel sulfate and citric acid are compounded to form a first solution. Specifically, lactic acid is taken in a beaker, 100ml of distilled water is added for full mixing, nickel sulfate is weighed in the beaker, citric acid is added, and a glass rod is used for continuously stirring until the nickel sulfate is completely dissolved to form a uniform transparent solution, so that a first solution is prepared.
(1.2) preparing a second solution: mixing sodium hypophosphite and sodium acetate to prepare a second solution. Specifically, the method comprises the following steps: weighing sodium hypophosphite in another beaker, adding 100ml of distilled water to fully dissolve the sodium hypophosphite, taking sodium acetate in the beaker, and stirring with a glass rod in the same way until a stable and uniform solution is formed to prepare a second solution.
(1.3) mixing the first solution and the second solution to a constant volume of 250ml, and adjusting the pH value to 4.5 to prepare the plating solution.
Wherein the mass ratio of the lactic acid to the nickel sulfate to the citric acid to the sodium hypophosphite to the sodium acetate is as follows: 40.8: 37: 5: 27: 18;
(12) and (3) placing the purified substrate sample in the plating solution in the step (11), stirring the plating solution at the rotating speed of 120r/min, sealing the opening of a container filled with the plating solution, and adjusting the pH of the plating solution every 20min to keep the pH at 4.5. Plating at 79 deg.C for 2.5h, cleaning, and drying.
The procedure for the purification treatment of the substrate sample was the same as in example 3.
(13) And (3) taking a phosphoric acid solution with the concentration of 2mol/L as an electrolyte, etching the base material sample obtained in the step (12) for 40min at the temperature of 22 ℃ and the voltage of 0.8V, cleaning and drying to obtain the nano porous nickel-phosphorus material.
2. And (3) catalytic reaction:
placing the nano porous nickel-phosphorus material prepared by the method in a constant temperature area of a tube furnace, firstly evacuating a quartz tube by using inert gas, then heating to 600 ℃ at the speed of 4 ℃/min in 90sccm inert atmosphere, preserving heat for 10min, and closing the inert gas. The inert gas is preferably nitrogen, and may be helium, neon, argon, or the like. Acetylene of 80sccm was introduced and reacted for 45 min. And after the reaction is finished, cooling to room temperature in a nitrogen atmosphere to obtain the spiral carbon nanofiber.
Comparative example 3:
this comparative example is partially the same as example 3, but the plated substrate was not subjected to the etching reaction of step (13). The method comprises the following specific steps:
1. preparing a nano porous nickel-phosphorus material:
(11) preparing a plating solution:
(1.1) preparation of modified carbon Black: placing the carbon black in concentrated nitric acid, heating in an oil bath at 90 ℃, condensing, refluxing, and stirring for reacting for 18 hours to obtain the modified carbon black. Cooling to room temperature, centrifugally washing to neutrality and drying for later use.
(1.2) preparing a first solution: lactic acid, nickel sulfate and citric acid are compounded to form a first solution. Specifically, lactic acid is taken in a beaker, 100ml of distilled water is added for full mixing, nickel sulfate is weighed in the beaker, citric acid is added, and a glass rod is used for continuously stirring until the nickel sulfate is completely dissolved to form a uniform transparent solution, so that a first solution is prepared.
(1.3) preparing a second solution: mixing sodium hypophosphite and sodium acetate to prepare a second solution. Specifically, the method comprises the following steps: weighing sodium hypophosphite in another beaker, adding 100ml of distilled water to fully dissolve the sodium hypophosphite, taking sodium acetate in the beaker, and stirring with a glass rod in the same way until a stable and uniform solution is formed to prepare a second solution.
(1.4) mixing the first solution and the second solution to a constant volume of 250ml, adding modified carbon black, carrying out ultrasonic oscillation for 25min, and adjusting the pH value to 4.5 to obtain the plating solution.
Wherein the mass ratio of the lactic acid to the nickel sulfate to the citric acid to the sodium hypophosphite to the sodium acetate to the modified carbon black is as follows: 40.8: 37: 5: 27: 18: 0.04;
(12) and (3) placing the purified substrate sample in the plating solution in the step (11), stirring the plating solution at the rotating speed of 120r/min, sealing the opening of a container filled with the plating solution, and adjusting the pH of the plating solution every 20min to keep the pH at 4.5. Plating at 79 deg.C for 2.5h, cleaning, and drying.
The procedure for the purification treatment of the substrate sample was the same as in example 3.
2. And (3) catalytic reaction:
placing the nano porous nickel-phosphorus material prepared by the method in a constant temperature area of a tube furnace, firstly evacuating a quartz tube by using inert gas, then heating to 600 ℃ at the speed of 4 ℃/min in 90sccm inert atmosphere, preserving heat for 10min, and closing the inert gas. The inert gas is preferably nitrogen, and may be helium, neon, argon, or the like. Acetylene of 80sccm was introduced and reacted for 45 min. And after the reaction is finished, cooling to room temperature in a nitrogen atmosphere to obtain the spiral carbon nanofiber.
Comparative example 4:
this comparative example is essentially the same as example 3, but no modification treatment was performed on the carbon black. The method comprises the following specific steps:
1. preparing a nano porous nickel-phosphorus material:
(11) preparing a plating solution:
(1.1) preparing a first solution: lactic acid, nickel sulfate and citric acid are compounded to form a first solution. Specifically, lactic acid is taken in a beaker, 100ml of distilled water is added for full mixing, nickel sulfate is weighed in the beaker, citric acid is added, and a glass rod is used for continuously stirring until the nickel sulfate is completely dissolved to form a uniform transparent solution, so that a first solution is prepared.
(1.2) preparing a second solution: mixing sodium hypophosphite and sodium acetate to prepare a second solution. Specifically, the method comprises the following steps: weighing sodium hypophosphite in another beaker, adding 100ml of distilled water to fully dissolve the sodium hypophosphite, taking sodium acetate in the beaker, and stirring with a glass rod in the same way until a stable and uniform solution is formed to prepare a second solution.
(1.3) mixing the first solution and the second solution to a constant volume of 250ml, adding carbon black, ultrasonically oscillating for 25min, and adjusting the pH value to 4.5 to obtain the plating solution.
Wherein the mass ratio of the lactic acid to the nickel sulfate to the citric acid to the sodium hypophosphite to the sodium acetate to the carbon black is as follows: 40.8: 37: 5: 27: 18: 0.04;
(12) and (3) placing the purified substrate sample in the plating solution in the step (11), stirring the plating solution at the rotating speed of 120r/min, sealing the opening of a container filled with the plating solution, and adjusting the pH of the plating solution every 20min to keep the pH at 4.5. Plating at 79 deg.C for 2.5h, cleaning, and drying.
The procedure for the purification treatment of the substrate sample was the same as in example 3.
(13) And (3) taking a phosphoric acid solution with the concentration of 2mol/L as an electrolyte, etching the base material sample obtained in the step (12) for 40min at the temperature of 22 ℃ and the voltage of 0.8V, cleaning and drying to obtain the nano porous nickel-phosphorus material.
2. And (3) catalytic reaction:
placing the nano porous nickel-phosphorus material prepared by the method in a constant temperature area of a tube furnace, firstly evacuating a quartz tube by using inert gas, then heating to 600 ℃ at the speed of 4 ℃/min in 90sccm inert atmosphere, preserving heat for 10min, and closing the inert gas. The inert gas is preferably nitrogen, and may be helium, neon, argon, or the like. Acetylene of 80sccm was introduced and reacted for 45 min. And after the reaction is finished, cooling to room temperature in a nitrogen atmosphere to obtain the spiral carbon nanofiber.
Test example:
the growth of the spiral carbon nanofibers prepared in examples 1 to 3 and comparative examples 1 to 4 was observed, and the microscopic morphology of the prepared spiral carbon nanofibers was observed by using a scanning electron microscope, which is described by taking example 3 as an example.
Fig. 1 is a scanning electron microscope image of a spiral filamentous nanocarbon manufactured in example 3, and fig. 2 is a scanning electron microscope image of example 3. As can be seen from FIG. 2, the carbon fiber is spiral and continuous and has uniform thickness, and the fiber diameter is measured to be 150-350nm, the spiral diameter is measured to be 400nm, and the spiral pitch is measured to be 400 nm.
Fig. 3 is a spiral filamentous nanocarbon manufactured in comparative example 1. Comparing fig. 1 and fig. 3, it can be seen that the carbon fiber prepared in example 3 covers the whole substrate sample in a dense state, and the spiral carbon nanofibers are grown on the surface of the substrate sample shown in fig. 3 only in sporadic places. It is shown that under the same conditions, the carbon black obtained after modification and the anodic electrochemical etching reaction can greatly improve the yield of carbon fibers.
Fig. 4 a spiral filamentous nanocarbon prepared in comparative example 2. Comparative example 2 corresponds to the addition of an anodic oxidation etching step to comparative example 1. As can be seen from fig. 4, the carbon fiber grown in comparative example 2 is significantly increased compared to that grown in comparative example 1, which shows that the yield of the carbon fiber can be significantly increased by anodic oxidation, but is still not as high as that of the carbon fiber produced in example 3, because no carbon black is added to the plating solution, so that the pores formed on the plating layer during etching are small and very uneven, which is not favorable for the growth of the carbon fiber in the subsequent catalytic reaction stage.
Fig. 5 shows a spiral filamentous nanocarbon obtained by comparative example 3. Comparative example 3 corresponds to the addition of modified carbon black to comparative example 1. As can be seen from FIG. 5, the carbon fiber grown in comparative example 3 is significantly increased compared to that grown in comparative example 1, indicating that the addition of modified carbon black to the plating solution can significantly improve the yield of carbon fiber, but still not as high as the yield of carbon fiber produced in example 3, due to the lack of anodic oxidation etching reaction, resulting in the reduction of pores on the surface of the nickel phosphorus material that are beneficial for the growth of carbon fiber.
Fig. 6 shows a spiral filamentous nanocarbon obtained by comparative example 4. Comparative example 4 corresponds to the addition of carbon black and an anodic oxidation etching step to comparative example 1. As can be seen from fig. 6, the carbon fibers grown in comparative example 4 are significantly increased compared to those grown in comparative example 1, comparative example 2 and comparative example 3, which shows that the carbon black and anodic oxidation etching steps can significantly improve the yield of the carbon fibers, but the yield of the carbon fibers is still not as high as that of the carbon fibers obtained in example 3, because the carbon black is not modified, the pores on the surface of the nickel-phosphorus material, which are beneficial to the growth of the carbon fibers, are less than those of the nano-porous nickel-phosphorus material treated by the modified carbon black, and further, the modified carbon black can improve the yield of the carbon.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A method for preparing a spiral carbon nanofiber, comprising:
(1) preparing a nano porous nickel-phosphorus material:
(11) placing the carbon black in concentrated nitric acid, heating in an oil bath at the temperature of 80-100 ℃, condensing, refluxing, and stirring for reaction for 15-20 hours to obtain modified carbon black; mixing lactic acid, nickel sulfate and citric acid to prepare a first solution, and mixing sodium hypophosphite and sodium acetate to prepare a second solution; mixing the first solution and the second solution to a constant volume, adding the modified carbon black, performing ultrasonic oscillation for 20-30 min, and adjusting the pH value to 4-5 to prepare a plating solution;
wherein the mass ratio of the lactic acid to the nickel sulfate to the citric acid to the sodium hypophosphite to the sodium acetate to the modified carbon black is as follows: (36-48): (30-45): (2-8): (20-35): (15-25): (0.01 to 0.1);
(12) placing the purified substrate sample in the plating solution obtained in the step (11), stirring the plating solution, plating for 2-3h at the temperature of 70-85 ℃, cleaning and drying;
(13) taking a phosphoric acid solution with the concentration of 1-5 mol/L as an electrolyte, etching the substrate sample obtained in the step (12) for 30-50 min at the temperature of 20-25 ℃ and the voltage of 0.5-1V, cleaning and drying to obtain the nano porous nickel-phosphorus material;
(2) and (3) raising the nano porous nickel-phosphorus material to 500-700 ℃ at the speed of 2-8 ℃/min in an inert atmosphere, preserving the heat for 8-15 min, and then introducing acetylene to react for 20-60 min to obtain the spiral carbon nanofiber.
2. The method for preparing a spiral filamentous nanocarbon according to claim 1, wherein in the step (12), the pH of the plating solution is adjusted every 10 to 30 min.
3. The method for preparing a spiral filamentous nanocarbon according to claim 1, wherein in the step (12), the plating solution is stirred at a rotation speed of 100 to 140r/min during plating, and a mouth of a container containing the plating solution is sealed.
4. The method for producing a spiral filamentous nanocarbon according to claim 1, wherein in the step (12), the step of purifying the substrate sample comprises:
s1: grinding and polishing the cut substrate sample;
s2: placing a substrate sample in an alkaline degreasing liquid, soaking for 10-20 min at 60-90 ℃, and then cleaning;
s3: and (3) placing the substrate sample into an acid rust removing solution, soaking for 3-7 min at the temperature of 20-40 ℃, and then cleaning.
5. The method for preparing spiral carbon nanofibers according to claim 4, wherein the alkaline degreasing fluid comprises the following components in a mass ratio of (3.5-4.5) to (3-5): (3.5-4.5) sodium hydroxide, sodium carbonate and sodium phosphate.
6. The method for preparing a spiral carbon nanofiber as claimed in claim 4, wherein the acidic rust removing solution is a hydrochloric acid solution with a volume concentration of 5-20%.
7. The method for producing a helical filamentous nanocarbon according to any one of claims 1 to 6, wherein the inert atmosphere is a nitrogen gas at a flow rate of 80 to 100 sccm.
8. The method for producing a spiral filamentous nanocarbon according to claim 7, wherein the aeration rate of acetylene is 60 to 100 sccm.
9. The spiral filamentous nanocarbon produced by the method according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810589099.1A CN108624992B (en) | 2018-06-08 | 2018-06-08 | Spiral nano carbon fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810589099.1A CN108624992B (en) | 2018-06-08 | 2018-06-08 | Spiral nano carbon fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108624992A CN108624992A (en) | 2018-10-09 |
| CN108624992B true CN108624992B (en) | 2020-10-09 |
Family
ID=63691303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810589099.1A Active CN108624992B (en) | 2018-06-08 | 2018-06-08 | Spiral nano carbon fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108624992B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161990B (en) * | 2018-09-10 | 2020-12-15 | 临沂大学 | Double-helix carbon fiber and preparation method thereof |
| CN112210868A (en) * | 2020-09-27 | 2021-01-12 | 高文灿 | Protective fabric and preparation method and application thereof |
| CN114361420A (en) * | 2022-01-10 | 2022-04-15 | 四川轻化工大学 | Spiral nano carbon fiber composite material, preparation method thereof and lithium battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500959C (en) * | 2006-01-06 | 2009-06-17 | 北京化工大学 | Method for preparing spiral nano carbon fiber |
| CN101451278B (en) * | 2007-12-03 | 2011-03-16 | 西北工业大学 | Method for preparing helical carbon fiber |
| JP2009140667A (en) * | 2007-12-04 | 2009-06-25 | Canon Inc | Solid polymer fuel cell, and manufacturing method thereof |
| CN105522781A (en) * | 2014-12-25 | 2016-04-27 | 比亚迪股份有限公司 | Metal base subjected to surface treatment, metal-resin compound, preparation methods and uses of metal-resin compound and metal base subjected to surface treatment, electronic product housing and preparation method of electronic product housing |
| CN104673321B (en) * | 2015-02-11 | 2019-05-31 | 博天环境集团股份有限公司 | A kind of heavy metals immobilization stabilizer and preparation method thereof and application method |
-
2018
- 2018-06-08 CN CN201810589099.1A patent/CN108624992B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108624992A (en) | 2018-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108624992B (en) | Spiral nano carbon fiber and preparation method thereof | |
| JP4151884B2 (en) | Method for producing a material in which a composite metal oxide nanomaterial is formed on a solid surface | |
| KR101591454B1 (en) | Manufacturing method for Metal and Oxide hybrid coated Nano Carbon | |
| CN104310372A (en) | Method for directly growing carbon nano tube array on fiber substrate | |
| KR20110131715A (en) | Method for preparing carbon nanofibers | |
| CN107572509B (en) | Nitrogen-doped hollow carbon/graphite nodule nano material and preparation method thereof | |
| Wu et al. | One-step synthesis of hierarchical metal oxide nanosheet/carbon nanotube composites by chemical vapor deposition | |
| Ren et al. | Study on the superhydrophilicity of the SiO 2-TiO 2 thin films prepared by sol-gel method at room temperature | |
| CN109811328A (en) | A kind of preparation method of boron-doped diamond film | |
| CN113148994B (en) | Graphene and preparation method and application thereof | |
| CN104357841B (en) | Iron-group carbide nano crystal-graphene nanoribbon composite material as well as preparation and application thereof | |
| Caceres-Ferreira et al. | The role of nitrogen plasma surface treatment and TiO2 seeding onto carbon fibers on the microwave-assisted growth of radially aligned TiO2 nanowires | |
| CN106893997B (en) | Nano-diamond film preparation substrate pre-treatment method | |
| CN100443629C (en) | Diamond thin-film reinforcement on tantalum spinning head surface by chemical gas phase deposition | |
| CN111943722A (en) | Controllable method for synthesizing carbon nano tube on surface of foamed ceramic and application thereof | |
| CN114748939B (en) | Preparation method of composite modified quartz sand filter material with multilevel structure | |
| CN114655945A (en) | Carbon nano tube surface coated amorphous or crystalline chromium oxide nano functional coating and preparation method and application thereof | |
| CN113684679B (en) | Preparation method and application of carbon fiber-based nanocomposite | |
| KR100461966B1 (en) | Carbon nano tube electrode electrochemical double layer capacitor using the same and fabricationa method thereof | |
| CN115069238A (en) | Single manganese metal catalyst and preparation method and application thereof | |
| KR100664751B1 (en) | Preparation of titania nanotubes | |
| KR100769992B1 (en) | Purification solution for carbon nano tube and method for purifying carbon nano tube thereby | |
| CN112194115A (en) | Preparation method of hollow carbon nanospheres and hollow carbon nanospheres | |
| CN111943169B (en) | Method for preparing metal-free carbon nano fiber by stripping method | |
| KR101201623B1 (en) | One-pot synthesis of silica nanoparticle in silica nanotube nano-structure |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |