CN108624992A - A kind of spiral nanometer carbon fiber and preparation method thereof - Google Patents
A kind of spiral nanometer carbon fiber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of spiral nanometer carbon fibers and preparation method thereof, belong to technical field of carbon fiber preparation.The present invention adds modified carbon black in the plating solution for preparing nickel-phosphorus coating, help to form more uniform nanovoids on nickel-phosphorus coating in etch phase by the modified carbon black particle of concentrated nitric acid oxidation, improve catalytic activity, and then advantageous growing environment is provided for the growth of follow-up spiral nanometer carbon fiber, realize the magnanimity growth of spiral nanometer carbon fiber.The present invention etches nickel-phosphorus coating using anodic oxidation engraving method, it is with stronger handling, the technological parameters such as concentration of electrolyte, voltage or electric current, time can strictly be controlled, to effectively avoid the prior art using the problem not easy to control of the reaction rate caused by chemical etching, realize prepared by the controllable process of nanoporous nickel phosphate material.Spiral nanometer carbon fiber pattern produced by the present invention is good, and yield is high, simple for process, and repeatability is high.
Description
Technical field
The present invention relates to technical field of carbon fiber preparation, and in particular to a kind of spiral nanometer carbon fiber and preparation method thereof.
Background technology
Spiral nanometer carbon fiber is a kind of material that performance is very excellent, and special helical form form makes it have high ratio
The excellent physics such as surface area, high ratio modulus, high conductivity, low-density and high resiliency, chemical property are expected to have in many fields
There is new potential application, for example high-performance electric electro-magnetic wave absorption device, height ratio capacity battery, touch sensor, nano-electromechanical are set
Standby and hydrogen-storing device etc..
Currently, both at home and abroad about preparing the method for spiral nanometer carbon fiber mostly based on chemical vapour deposition technique (CVD),
It uses graphite or ceramics as matrix, then spreads catalyst particle in matrix, being passed through hydrocarbon gas under high-temperature atmosphere is urged
Change pyrolysis, spiral nanometer carbon fiber is precipitated on the catalyst particles.The higher spiral of purity can be prepared by such method to receive
Rice carbon fiber, but such method is often influenced by catalyst granules very big, the spiral nanometer carbon fiber after growth is generally deposited
In low output, complex process, of high cost.
Invention content
The purpose of the present invention is to provide a kind of spiral nanometer carbon fibers and preparation method thereof, to solve existing preparation method
Complex process, cannot achieve the problem of mass production at of high cost, low output.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of preparation method of spiral nanometer carbon fiber, including：
(1) nanoporous nickel phosphate material is prepared：
(11) carbon black is placed in concentrated nitric acid and is heated in 80~100 DEG C of oil bath, condensing reflux, it is stirred to react 15~
Modified carbon black is made in 20h；By lactic acid, nickel sulfate and citric acid with the first solution is mixed and made into, by sodium hypophosphite and sodium acetate
It is hybridly prepared into the second solution；By the first solution and the second solution mixing constant volume, it is added modified carbon black, ultrasonic vibration 20~
PH to 4~5 is adjusted after 30min, and plating solution is made；
Wherein, the mass ratio of lactic acid, nickel sulfate, citric acid, sodium hypophosphite, sodium acetate and modified carbon black is：(36~
48)：(30~45)：(2~8)：(20~35)：(15~25)：(0.01~0.1)；
(12) substrate coupons Jing Guo purified treatment are placed in the plating solution of step (11), plating solution are stirred, at 70~85 DEG C
2~3h of lower plating, cleaning, drying；
(13) using the phosphoric acid solution of a concentration of 1~5mol/L as electrolyte, the substrate coupons that step (12) obtains are existed
30~50min, cleaning, dry, obtained nanoporous nickel phosphorus are etched under conditions of temperature is 20~25 DEG C, voltage is 0.5~1V
Material；
(2) the nanoporous nickel phosphate material is risen to 500~700 DEG C in inert atmosphere with the rate of 2~8 DEG C/min
And 8~15min is kept the temperature, 20~60min of acetylene reaction is then passed to, spiral nanometer carbon fiber is made.
The present invention is prepared by design technology step, adjusting technological parameter and raw material proportioning conducive to spiral nanometer carbon fiber
The nanoporous nickel phosphate material for tieing up growth, to realize the magnanimity growth of spiral nanometer carbon fiber.Specifically：
First, the present invention adds modified carbon black in the plating solution for preparing nickel-phosphorus coating, modified by concentrated nitric acid oxidation
Carbon black particle helps to form more uniform nanovoids on nickel-phosphorus coating in etch phase, improves catalytic activity, in turn
Advantageous growing environment is provided for the growth of follow-up spiral nanometer carbon fiber.And the present invention is by nitric acid oxidation modification
Nano carbon black particle can significantly improve the stability of the dispersibility and plating solution of carbon black particle in the plating solution, can make carbon black
Nano surface pore structure smaller, more uniformity have higher specific surface area, play higher catalytic performance, real
The magnanimity growth of existing spiral nanometer carbon fiber.
Secondly, the present invention is etched nickel-phosphorus coating obtained, makes its rough surface, further increases spiral nanometer carbon
The increment of fiber, and the present invention etches nickel-phosphorus coating using anodic oxidation engraving method, with stronger handling, energy
The technological parameters such as enough stringent control concentration of electrolyte, voltage or electric current, time, to effectively avoid the prior art from being lost using chemistry
The problem that reaction rate caused by carving is difficult to control realizes prepared by the controllable process of nanoporous nickel phosphate material.In addition to this,
The present invention prepares the first solution and the second solution when preparing plating solution respectively, will be as the nickel sulfate of oxidant and as reducing agent
Sodium hypophosphite it is separately formulated, avoid reaction from just being carried out in advance in process for preparation, realize further control to reaction, carry
The controllability of high preparation process.
Further, in step (12), the pH of plating solution is adjusted every 10~30min.
The present invention can overcome the due to of being carried out because reacting that pH is caused to reduce by carrying out continual adjusting pH value to plating solution
Defect, to ensure the stability of plating solution.
Further, in step (12), plating solution is stirred with the rotating speed of 100~140r/min in plating, and will be equipped with
The container finish of plating solution seals.
By stirring so that reacting the more abundant of progress；Plating solution in reaction process can be reduced by sealing container bottleneck
Evaporation.
Further, in step (12), the purified treatment step of substrate coupons includes：
S1：Substrate coupons after cutting are polished, are polished；
S2：Substrate coupons are placed in alkaline degreasing liquid 10~20min of immersion under conditions of 60~90 DEG C, then clearly
It washes；
S3：Substrate coupons are placed in acidic derusting liquid 3~7min of immersion under conditions of 20~40 DEG C, are then cleaned.
By polish, polish make substrate coupons surface it is more smooth contribute to reaction be smoothed out, coating is formed, use simultaneously
Parlkaline degreasing fluid, which cleans the substrate coupons after sanding and polishing, can obtain bright, smooth, fine and close nickel phosphorus carbon alloy
Coating, further assisted reaction are smoothed out.Further, since substrate coupons are generally steel, it is easy in air by oxygen
Change, therefore the present invention is further cleaned by acidic derusting liquid, can both be derusted, and specimen surface, being conducive to can also be activated
Plating reaction is learned to be smoothed out.
Further, it is (3.5~4.5) that above-mentioned alkaline degreasing liquid, which includes mass ratio,:(3~5)：The hydrogen-oxygen of (3.5~4.5)
Change sodium, sodium carbonate and sodium phosphate.
Further, above-mentioned acidic derusting liquid is the hydrochloric acid solution that volumetric concentration is 5~20%.
Further, the Ventilation Rate of above-mentioned inert atmosphere is 80~100sccm, and inert atmosphere is nitrogen.
Further, the Ventilation Rate of above-mentioned acetylene is 60~100sccm.
The spiral nanometer carbon fiber that above-mentioned method is prepared.
The invention has the advantages that：
The present invention has given full play to the activity of nanoporous nickel phosphate material, realizes the magnanimity growth of spiral nanometer carbon fiber,
The spiral nanometer carbon fiber pattern grown is good, and yield is high, and simple for process, controllability is good, and repeatability is high.
The modified carbon black particle of nitric acid oxidation is introduced into nickel-phosphorus coating by the present invention, is kept its dispersibility more preferable, is prepared
The nanoporous nickel material gone out has unique even pore structure, the catalytic activity played stronger.The present invention uses erosion
Nanoporous nickel phosphate material after quarter, can magnanimity growth spiral compared with not etched Ni-P-C alloys as catalyst
Carbon nano-fiber.
Description of the drawings
Fig. 1 is the growing state photo of spiral nanometer carbon fiber prepared by embodiment 3；
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 3；
Fig. 3 is the growing state photo of spiral nanometer carbon fiber prepared by comparative example 1；
Fig. 4 is the growing state photo of spiral nanometer carbon fiber prepared by comparative example 2；
Fig. 5 is the growing state photo of spiral nanometer carbon fiber prepared by comparative example 3；
Fig. 6 is the growing state photo of spiral nanometer carbon fiber prepared by comparative example 4.
Specific implementation mode
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.The person that is not specified actual conditions in embodiment, the item suggested according to normal condition or manufacturer
Part carries out.Reagents or instruments used without specified manufacturer is the conventional products that can be obtained by commercially available purchase.
Embodiment 1：
The preparation method of the spiral nanometer carbon fiber of the present embodiment, including：
1, nanoporous nickel phosphate material is prepared：
(11) plating solution is prepared：
(1.1) modified carbon black is prepared：Carbon black is placed in concentrated nitric acid and is heated in 80 DEG C of oil bath, condensing reflux stirs
Reaction 20h is mixed, modified carbon black is made.It is cooled to room temperature, dried for standby after centrifuge washing to neutrality.
(1.2) the first solution is prepared：Lactic acid, nickel sulfate and citric acid are matched and are mixed and made into the first solution.Specifically, breast is taken
Acid is added 100ml distilled water and is sufficiently mixed in beaker, then weighs nickel sulfate in beaker, and citric acid is added and uses glass bar simultaneously
It is stirred continuously, until nickel sulfate is completely dissolved to form homogeneous transparent degree solution, the first solution is made.
(1.3) the second solution is prepared：Sodium hypophosphite and sodium acetate are hybridly prepared into the second solution.Specifically：Another
Sodium hypophosphite is weighed in one beaker, 100ml distilled water, which is added, makes sodium hypophosphite fully dissolve, then takes sodium acetate in beaker
In, it is equally stirred with glass bar, until forming the solution of stable and uniform, the second solution is made.
(1.4) above-mentioned first solution and the second solution are mixed and is settled to 250ml, modified carbon black, ultrasonic vibration is added
PH to 4 is adjusted after 20min, and plating solution is made.
Wherein, the mass ratio of lactic acid, nickel sulfate, citric acid, sodium hypophosphite, sodium acetate and modified carbon black is：36：
32.8：3：23.2：16.4：0.02；
(12) substrate coupons Jing Guo purified treatment are placed in the plating solution of step (11), are stirred with the rotating speed of 100r/min
Plating solution seals the container finish equipped with plating solution, every the pH that 10min adjusts plating solution, is allowed to be maintained at 4.The plating at 70 DEG C
3h, cleaning, drying.
The purified treatment step of substrate coupons includes：
S1：Substrate coupons after cutting are polished, are polished；Processing cuts into 10mm × 10mm × 3mm samples.First exist
Specimen surface and section are slightly polished on polishing machine, until smooth-out.Smart polishing is carried out on sand paper again, until plane
Occur bright luster and cut it is less (sand paper grinding turn be 200# → 400# → 600# → 800# → 1000# → 1200# →
1400#→1600#→2000#)。
S2：It is 3.5 that substrate coupons, which are placed in mass ratio,：3：What 3.5 sodium hydroxide, sodium carbonate and sodium phosphate was formulated
In 100ml alkaline degreasing liquid, 20min is impregnated under conditions of 60 DEG C, is then cleaned；
S3：Substrate coupons are placed in the hydrochloric acid solution that volumetric concentration is 5% and impregnate 3min under conditions of 40 DEG C, then
Cleaning.
(13) using the phosphoric acid solution of a concentration of 1mol/L as electrolyte, the substrate coupons that step (12) is obtained are in temperature
50min, cleaning, dry, the obtained nanoporous nickel phosphate material are etched under conditions of being 0.5V for 20 DEG C, voltage.
2, catalysis reaction：
By nanoporous nickel phosphate material made from the above method in the flat-temperature zone for being placed in tube furnace, first use inert gas will
Quartz ampoule empties, and is then warming up to 500 DEG C in the inert atmosphere of 80sccm with the rate of 2 DEG C/min, keeps the temperature 15min, closes
Inert gas.Inert gas is preferably nitrogen, can also be helium, neon, argon gas etc..It is passed through the acetylene reaction of 60sccm
60min.It is cooled to room temperature in a nitrogen atmosphere after reaction, spiral nanometer carbon fiber is made.
Embodiment 2：
The preparation method of the spiral nanometer carbon fiber of the present embodiment, including：
1, nanoporous nickel phosphate material is prepared：
(11) plating solution is prepared：
(1.1) modified carbon black is prepared：Carbon black is placed in concentrated nitric acid and is heated in 100 DEG C of oil bath, condensing reflux stirs
Reaction 15h is mixed, modified carbon black is made.It is cooled to room temperature, dried for standby after centrifuge washing to neutrality.
(1.2) the first solution is prepared：Lactic acid, nickel sulfate and citric acid are matched and are mixed and made into the first solution.Specifically, breast is taken
Acid is added 100ml distilled water and is sufficiently mixed in beaker, then weighs nickel sulfate in beaker, and citric acid is added and uses glass bar simultaneously
It is stirred continuously, until nickel sulfate is completely dissolved to form homogeneous transparent degree solution, the first solution is made.
(1.3) the second solution is prepared：Sodium hypophosphite and sodium acetate are hybridly prepared into the second solution.Specifically：Another
Sodium hypophosphite is weighed in one beaker, 100ml distilled water, which is added, makes sodium hypophosphite fully dissolve, then takes sodium acetate in beaker
In, it is equally stirred with glass bar, until forming the solution of stable and uniform, the second solution is made.
(1.4) above-mentioned first solution and the second solution are mixed and is settled to 250ml, modified carbon black, ultrasonic vibration is added
PH to 5 is adjusted after 30min, and plating solution is made.
Wherein, the mass ratio of lactic acid, nickel sulfate, citric acid, sodium hypophosphite, sodium acetate and modified carbon black is：45：42：
7.5：32：22：0.08；
(12) substrate coupons Jing Guo purified treatment are placed in the plating solution of step (11), are stirred with the rotating speed of 140r/min
Plating solution seals the container finish equipped with plating solution, every the pH that 30min adjusts plating solution, is allowed to be maintained at 5.The plating at 85 DEG C
2h, cleaning, drying.
The purified treatment step of substrate coupons includes：
S1：Substrate coupons after cutting are polished, are polished；
S2：It is 4.5 that substrate coupons, which are placed in mass ratio,：5：What 4.5 sodium hydroxide, sodium carbonate and sodium phosphate was formulated
In 100ml alkaline degreasing liquid, 10min is impregnated under conditions of 90 DEG C, is then cleaned；
S3：Substrate coupons are placed in the hydrochloric acid solution that volumetric concentration is 20% and impregnate 7min under conditions of 20 DEG C, so
After clean.
(13) using the phosphoric acid solution of a concentration of 5mol/L as electrolyte, the substrate coupons that step (12) is obtained are in temperature
30min, cleaning, dry, the obtained nanoporous nickel phosphate material are etched under conditions of being 1V for 25 DEG C, voltage.
2, catalysis reaction：
By nanoporous nickel phosphate material made from the above method in the flat-temperature zone for being placed in tube furnace, first use inert gas will
Quartz ampoule empties, and is then warming up to 700 DEG C in the inert atmosphere of 100sccm with the rate of 8 DEG C/min, keeps the temperature 8min, closes
Inert gas.Inert gas is preferably nitrogen, can also be helium, neon, argon gas etc..It is passed through the acetylene reaction of 100sccm
20min.It is cooled to room temperature in a nitrogen atmosphere after reaction, spiral nanometer carbon fiber is made.
Embodiment 3：
The preparation method of the spiral nanometer carbon fiber of the present embodiment, including：
1, nanoporous nickel phosphate material is prepared：
(11) plating solution is prepared：
(1.1) modified carbon black is prepared：Carbon black is placed in concentrated nitric acid and is heated in 90 DEG C of oil bath, condensing reflux stirs
Reaction 18h is mixed, modified carbon black is made.It is cooled to room temperature, dried for standby after centrifuge washing to neutrality.
(1.2) the first solution is prepared：Lactic acid, nickel sulfate and citric acid are matched and are mixed and made into the first solution.Specifically, breast is taken
Acid is added 100ml distilled water and is sufficiently mixed in beaker, then weighs nickel sulfate in beaker, and citric acid is added and uses glass bar simultaneously
It is stirred continuously, until nickel sulfate is completely dissolved to form homogeneous transparent degree solution, the first solution is made.
(1.3) the second solution is prepared：Sodium hypophosphite and sodium acetate are hybridly prepared into the second solution.Specifically：Another
Sodium hypophosphite is weighed in one beaker, 100ml distilled water, which is added, makes sodium hypophosphite fully dissolve, then takes sodium acetate in beaker
In, it is equally stirred with glass bar, until forming the solution of stable and uniform, the second solution is made.
(1.4) above-mentioned first solution and the second solution are mixed and is settled to 250ml, modified carbon black, ultrasonic vibration is added
PH to 4.5 is adjusted after 25min, and plating solution is made.
Wherein, the mass ratio of lactic acid, nickel sulfate, citric acid, sodium hypophosphite, sodium acetate and modified carbon black is：40.8：
37：5：27：18：0.04；
(12) substrate coupons Jing Guo purified treatment are placed in the plating solution of step (11), are stirred with the rotating speed of 120r/min
Plating solution seals the container finish equipped with plating solution, every the pH that 20min adjusts plating solution, is allowed to be maintained at 4.5.It is applied at 79 DEG C
Plate 2.5h, cleaning, drying.
The purified treatment step of substrate coupons includes：
S1：Substrate coupons after cutting are polished, are polished；
S2：It is 4 that substrate coupons, which are placed in mass ratio,：3.8：What 4 sodium hydroxide, sodium carbonate and sodium phosphate was formulated
In 100ml alkaline degreasing liquid, 15min is impregnated under conditions of 80 DEG C, is then cleaned；
S3：Substrate coupons are placed in the hydrochloric acid solution that volumetric concentration is 10% and impregnate 5min under conditions of 30 DEG C, so
After clean.
(13) using the phosphoric acid solution of a concentration of 2mol/L as electrolyte, the substrate coupons that step (12) is obtained are in temperature
40min, cleaning, dry, the obtained nanoporous nickel phosphate material are etched under conditions of being 0.8V for 22 DEG C, voltage.
2, catalysis reaction：
By nanoporous nickel phosphate material made from the above method in the flat-temperature zone for being placed in tube furnace, first use inert gas will
Quartz ampoule empties, and is then warming up to 600 DEG C in the inert atmosphere of 90sccm with the rate of 4 DEG C/min, keeps the temperature 10min, closes
Inert gas.Inert gas is preferably nitrogen, can also be helium, neon, argon gas etc..It is passed through the acetylene reaction of 80sccm
45min.It is cooled to room temperature in a nitrogen atmosphere after reaction, spiral nanometer carbon fiber is made.
Comparative example 1：
This comparative example is identical as 3 part of embodiment, but lacks carbon black in plating solution, and the base material after plating does not carry out
The etching reaction of step (13).It is as follows：
1, nanoporous nickel phosphate material is prepared：
(11) plating solution is prepared：
(1.1) the first solution is prepared：Lactic acid, nickel sulfate and citric acid are matched and are mixed and made into the first solution.Specifically, breast is taken
Acid is added 100ml distilled water and is sufficiently mixed in beaker, then weighs nickel sulfate in beaker, and citric acid is added and uses glass bar simultaneously
It is stirred continuously, until nickel sulfate is completely dissolved to form homogeneous transparent degree solution, the first solution is made.
(1.2) the second solution is prepared：Sodium hypophosphite and sodium acetate are hybridly prepared into the second solution.Specifically：Another
Sodium hypophosphite is weighed in one beaker, 100ml distilled water, which is added, makes sodium hypophosphite fully dissolve, then takes sodium acetate in beaker
In, it is equally stirred with glass bar, until forming the solution of stable and uniform, the second solution is made.
(1.3) above-mentioned first solution and the second solution are mixed and is settled to 250ml, adjust pH to 4.5, plating solution is made.
Wherein, lactic acid, nickel sulfate, citric acid, sodium hypophosphite, sodium acetate mass ratio be：40.8：37：5：27：18；
(12) substrate coupons Jing Guo purified treatment are placed in the plating solution of step (11), are stirred with the rotating speed of 120r/min
Plating solution seals the container finish equipped with plating solution, every the pH that 20min adjusts plating solution, is allowed to be maintained at 4.5.It is applied at 79 DEG C
Plate 2.5h, cleaning, drying.
The purified treatment step of substrate coupons is same as Example 3.
2, catalysis reaction：
By nanoporous nickel phosphate material made from the above method in the flat-temperature zone for being placed in tube furnace, first use inert gas will
Quartz ampoule empties, and is then warming up to 600 DEG C in the inert atmosphere of 90sccm with the rate of 4 DEG C/min, keeps the temperature 10min, closes
Inert gas.Inert gas is preferably nitrogen, can also be helium, neon, argon gas etc..It is passed through the acetylene reaction of 80sccm
45min.It is cooled to room temperature in a nitrogen atmosphere after reaction, spiral nanometer carbon fiber is made.
Comparative example 2：
This comparative example is identical as 3 part of embodiment, but lacks carbon black in plating solution.It is as follows：
1, nanoporous nickel phosphate material is prepared：
(11) plating solution is prepared：
(1.1) the first solution is prepared：Lactic acid, nickel sulfate and citric acid are matched and are mixed and made into the first solution.Specifically, breast is taken
Acid is added 100ml distilled water and is sufficiently mixed in beaker, then weighs nickel sulfate in beaker, and citric acid is added and uses glass bar simultaneously
It is stirred continuously, until nickel sulfate is completely dissolved to form homogeneous transparent degree solution, the first solution is made.
(1.2) the second solution is prepared：Sodium hypophosphite and sodium acetate are hybridly prepared into the second solution.Specifically：Another
Sodium hypophosphite is weighed in one beaker, 100ml distilled water, which is added, makes sodium hypophosphite fully dissolve, then takes sodium acetate in beaker
In, it is equally stirred with glass bar, until forming the solution of stable and uniform, the second solution is made.
(1.3) above-mentioned first solution and the second solution are mixed and is settled to 250ml, adjust pH to 4.5, plating solution is made.
Wherein, lactic acid, nickel sulfate, citric acid, sodium hypophosphite, sodium acetate mass ratio be：40.8：37：5：27：18；
(12) substrate coupons Jing Guo purified treatment are placed in the plating solution of step (11), are stirred with the rotating speed of 120r/min
Plating solution seals the container finish equipped with plating solution, every the pH that 20min adjusts plating solution, is allowed to be maintained at 4.5.It is applied at 79 DEG C
Plate 2.5h, cleaning, drying.
The purified treatment step of substrate coupons is same as Example 3.
(13) using the phosphoric acid solution of a concentration of 2mol/L as electrolyte, the substrate coupons that step (12) is obtained are in temperature
40min, cleaning, dry, the obtained nanoporous nickel phosphate material are etched under conditions of being 0.8V for 22 DEG C, voltage.
2, catalysis reaction：
By nanoporous nickel phosphate material made from the above method in the flat-temperature zone for being placed in tube furnace, first use inert gas will
Quartz ampoule empties, and is then warming up to 600 DEG C in the inert atmosphere of 90sccm with the rate of 4 DEG C/min, keeps the temperature 10min, closes
Inert gas.Inert gas is preferably nitrogen, can also be helium, neon, argon gas etc..It is passed through the acetylene reaction of 80sccm
45min.It is cooled to room temperature in a nitrogen atmosphere after reaction, spiral nanometer carbon fiber is made.
Comparative example 3：
This comparative example is identical as 3 part of embodiment, but the base material after plating does not carry out the etching reaction of step (13).
It is as follows：
1, nanoporous nickel phosphate material is prepared：
(11) plating solution is prepared：
(1.1) modified carbon black is prepared：Carbon black is placed in concentrated nitric acid and is heated in 90 DEG C of oil bath, condensing reflux stirs
Reaction 18h is mixed, modified carbon black is made.It is cooled to room temperature, dried for standby after centrifuge washing to neutrality.
(1.2) the first solution is prepared：Lactic acid, nickel sulfate and citric acid are matched and are mixed and made into the first solution.Specifically, breast is taken
Acid is added 100ml distilled water and is sufficiently mixed in beaker, then weighs nickel sulfate in beaker, and citric acid is added and uses glass bar simultaneously
It is stirred continuously, until nickel sulfate is completely dissolved to form homogeneous transparent degree solution, the first solution is made.
(1.3) the second solution is prepared：Sodium hypophosphite and sodium acetate are hybridly prepared into the second solution.Specifically：Another
Sodium hypophosphite is weighed in one beaker, 100ml distilled water, which is added, makes sodium hypophosphite fully dissolve, then takes sodium acetate in beaker
In, it is equally stirred with glass bar, until forming the solution of stable and uniform, the second solution is made.
(1.4) above-mentioned first solution and the second solution are mixed and is settled to 250ml, modified carbon black, ultrasonic vibration is added
PH to 4.5 is adjusted after 25min, and plating solution is made.
Wherein, the mass ratio of lactic acid, nickel sulfate, citric acid, sodium hypophosphite, sodium acetate and modified carbon black is：40.8：
37：5：27：18：0.04；
(12) substrate coupons Jing Guo purified treatment are placed in the plating solution of step (11), are stirred with the rotating speed of 120r/min
Plating solution seals the container finish equipped with plating solution, every the pH that 20min adjusts plating solution, is allowed to be maintained at 4.5.It is applied at 79 DEG C
Plate 2.5h, cleaning, drying.
The purified treatment step of substrate coupons is same as Example 3.
2, catalysis reaction：
By nanoporous nickel phosphate material made from the above method in the flat-temperature zone for being placed in tube furnace, first use inert gas will
Quartz ampoule empties, and is then warming up to 600 DEG C in the inert atmosphere of 90sccm with the rate of 4 DEG C/min, keeps the temperature 10min, closes
Inert gas.Inert gas is preferably nitrogen, can also be helium, neon, argon gas etc..It is passed through the acetylene reaction of 80sccm
45min.It is cooled to room temperature in a nitrogen atmosphere after reaction, spiral nanometer carbon fiber is made.
Comparative example 4：
This comparative example is substantially the same manner as Example 3, but is not modified processing to carbon black.It is as follows：
1, nanoporous nickel phosphate material is prepared：
(11) plating solution is prepared：
(1.1) the first solution is prepared：Lactic acid, nickel sulfate and citric acid are matched and are mixed and made into the first solution.Specifically, breast is taken
Acid is added 100ml distilled water and is sufficiently mixed in beaker, then weighs nickel sulfate in beaker, and citric acid is added and uses glass bar simultaneously
It is stirred continuously, until nickel sulfate is completely dissolved to form homogeneous transparent degree solution, the first solution is made.
(1.2) the second solution is prepared：Sodium hypophosphite and sodium acetate are hybridly prepared into the second solution.Specifically：Another
Sodium hypophosphite is weighed in one beaker, 100ml distilled water, which is added, makes sodium hypophosphite fully dissolve, then takes sodium acetate in beaker
In, it is equally stirred with glass bar, until forming the solution of stable and uniform, the second solution is made.
(1.3) above-mentioned first solution and the second solution are mixed and is settled to 250ml, be added carbon black, after ultrasonic vibration 25min
PH to 4.5 is adjusted, plating solution is made.
Wherein, the mass ratio of lactic acid, nickel sulfate, citric acid, sodium hypophosphite, sodium acetate and carbon black is：40.8：37：5：
27：18：0.04；
(12) substrate coupons Jing Guo purified treatment are placed in the plating solution of step (11), are stirred with the rotating speed of 120r/min
Plating solution seals the container finish equipped with plating solution, every the pH that 20min adjusts plating solution, is allowed to be maintained at 4.5.It is applied at 79 DEG C
Plate 2.5h, cleaning, drying.
The purified treatment step of substrate coupons is same as Example 3.
(13) using the phosphoric acid solution of a concentration of 2mol/L as electrolyte, the substrate coupons that step (12) is obtained are in temperature
40min, cleaning, dry, the obtained nanoporous nickel phosphate material are etched under conditions of being 0.8V for 22 DEG C, voltage.
2, catalysis reaction：
By nanoporous nickel phosphate material made from the above method in the flat-temperature zone for being placed in tube furnace, first use inert gas will
Quartz ampoule empties, and is then warming up to 600 DEG C in the inert atmosphere of 90sccm with the rate of 4 DEG C/min, keeps the temperature 10min, closes
Inert gas.Inert gas is preferably nitrogen, can also be helium, neon, argon gas etc..It is passed through the acetylene reaction of 80sccm
45min.It is cooled to room temperature in a nitrogen atmosphere after reaction, spiral nanometer carbon fiber is made.
Test example：
The growing state that spiral nanometer carbon fiber is made in above-described embodiment 1-3 and comparative example 1-4 is observed, scanning electricity is used in combination
The microscopic appearance of spiral nanometer carbon fiber made from sem observation is illustrated by taking embodiment 3 as an example.
Fig. 1 is spiral nanometer carbon fiber made from embodiment 3, and Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 3.It can be with from Fig. 2
Find out, carbon fiber in the shape of a spiral and continuously, even thickness, through measuring, fibre diameter 150-350nm, screw diameter 400nm,
Helical pitch 400nm.
Fig. 3 is spiral nanometer carbon fiber made from comparative example 1.Comparison diagram 1 and Fig. 3 can be seen that carbon made from embodiment 3
Fiber covers entire substrate coupons, is in dense state, and substrate coupons surface shown in Fig. 3 only has fragmentary several places growth spiral shell
Revolve carbon nano-fiber.Illustrate, it is all identical in other conditions, it is modified to obtain carbon black and anode electrochemical etching reaction
The yield of carbon fiber can be greatly improved.
Spiral nanometer carbon fiber made from Fig. 4 comparative examples 2.Comparative example 2 is equivalent to increases sun on the basis of comparative example 1
Pole oxidizing etch step.From fig. 4, it can be seen that the carbon fiber showed increased that comparative example 2 is grown relative to comparative example 1, illustrates, sun
Pole, which aoxidizes, can significantly improve the yield of carbon fiber, but still high not as good as the carbon fiber yield obtained by embodiment 3, this be by
Without addition carbon black in plating solution so that the hole formed on coating in etching is few and extremely uneven, is unfavorable for subsequent catalyst
The growth of stage of reaction carbon fiber.
Spiral nanometer carbon fiber made from Fig. 5 comparative examples 3.Comparative example 3, which is equivalent to increase on the basis of comparative example 1, to be changed
Property carbon black.From fig. 5, it can be seen that the carbon fiber showed increased that comparative example 3 is grown relative to comparative example 1, illustrates, modified carbon black adds
The yield of carbon fiber can be significantly improved by adding in plating solution, but still high not as good as the carbon fiber yield obtained by embodiment 3, this
Be due to lacking anodic oxidation etching reaction, and cause nickel phosphate material surface be conducive to carbon fibre growth hole reduce.
Spiral nanometer carbon fiber made from Fig. 6 comparative examples 4.Comparative example 4 is equivalent to increases charcoal on the basis of comparative example 1
Black and anodic oxidation etching step.From fig. 6, it can be seen that comparative example 4 is relative to comparative example 1, comparative example 2 and comparative example 3
The equal showed increased of carbon fiber of growth, illustrates, carbon black and anodic oxidation etching step can significantly improve the yield of carbon fiber, but
It is still high not as good as the carbon fiber yield obtained by embodiment 3, this is because not to carbon black modified, and lead to nickel phosphate material surface
To lack compared with the nanoporous nickel phosphate material that modified carbon black is handled conducive to the hole of carbon fibre growth, further illustrate, it is modified
Carbon black can improve the yield of carbon fiber.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of spiral nanometer carbon fiber, which is characterized in that including：
(1) nanoporous nickel phosphate material is prepared：
(11) carbon black being placed in concentrated nitric acid and is heated in 80~100 DEG C of oil bath, condensing reflux is stirred to react 15~20h,
Modified carbon black is made；Lactic acid, nickel sulfate and citric acid are mixed and made into the first solution, sodium hypophosphite and sodium acetate are mixed and matched
The second solution is made；By the first solution and the second solution mixing constant volume, the modified carbon black, 20~30min of ultrasonic vibration is added
PH to 4~5 is adjusted afterwards, and plating solution is made；
Wherein, the mass ratio of lactic acid, nickel sulfate, citric acid, sodium hypophosphite, sodium acetate and modified carbon black is：(36~48)：
(30~45)：(2~8)：(20~35)：(15~25)：(0.01~0.1)；
(12) substrate coupons Jing Guo purified treatment are placed in the plating solution of step (11), stir plating solution, is applied at 70~85 DEG C
Plate 2-3h, cleaning, drying；
(13) using the phosphoric acid solution of a concentration of 1~5mol/L as electrolyte, the substrate coupons that step (12) is obtained are in temperature
30~50min, cleaning, dry, the obtained nanoporous nickel phosphorus are etched under conditions of being 0.5~1V for 20~25 DEG C, voltage
Material；
(2) the nanoporous nickel phosphate material is risen to 500~700 DEG C with the rate of 2~8 DEG C/min in inert atmosphere and protected
8~15min of temperature, then passes to 20~60min of acetylene reaction, and spiral nanometer carbon fiber is made.
2. the preparation method of spiral nanometer carbon fiber according to claim 1, which is characterized in that in step (12), every
10~30min adjusts the pH of plating solution.
3. the preparation method of spiral nanometer carbon fiber according to claim 1, which is characterized in that in step (12), applying
Plating solution is stirred with the rotating speed of 100~140r/min when plating, and the container finish equipped with plating solution is sealed.
4. the preparation method of spiral nanometer carbon fiber according to claim 1, which is characterized in that described in step (12)
The purified treatment step of substrate coupons includes：
S1：Substrate coupons after cutting are polished, are polished；
S2：Substrate coupons are placed in alkaline degreasing liquid 10~20min of immersion under conditions of 60~90 DEG C, are then cleaned；
S3：Substrate coupons are placed in acidic derusting liquid 3~7min of immersion under conditions of 20~40 DEG C, are then cleaned.
5. the preparation method of spiral nanometer carbon fiber according to claim 4, which is characterized in that the alkaline degreasing liquid packet
It is (3.5~4.5) to include mass ratio:(3~5)：Sodium hydroxide, sodium carbonate and the sodium phosphate of (3.5~4.5).
6. the preparation method of spiral nanometer carbon fiber according to claim 4, which is characterized in that the acidic derusting liquid is
The hydrochloric acid solution that volumetric concentration is 5~20%.
7. according to the preparation method of claim 1~6 any one of them spiral nanometer carbon fiber, which is characterized in that described lazy
Property atmosphere Ventilation Rate be 80~100sccm, inert atmosphere is nitrogen.
8. the preparation method of spiral nanometer carbon fiber according to claim 7, which is characterized in that the ventilation speed of the acetylene
Rate is 60~100sccm.
9. the spiral nanometer carbon fiber that claim 1~8 any one of them method is prepared.
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| CN109161990A (en) * | 2018-09-10 | 2019-01-08 | 临沂大学 | A kind of 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 |
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| CN109161990B (en) * | 2018-09-10 | 2020-12-15 | 临沂大学 | Double-helix carbon fiber and preparation method thereof |
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| 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 |
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