CN103696243A - Composite fiber material of nickel and carbon nano tubes and preparation method thereof - Google Patents
Composite fiber material of nickel and carbon nano tubes and preparation method thereof Download PDFInfo
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- CN103696243A CN103696243A CN201310645142.9A CN201310645142A CN103696243A CN 103696243 A CN103696243 A CN 103696243A CN 201310645142 A CN201310645142 A CN 201310645142A CN 103696243 A CN103696243 A CN 103696243A
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Abstract
The invention relates to a composite fiber material of nickel and carbon nano tubes and a preparation method thereof. The composite fiber is nano composite fiber of nickel and carbon nano tubes as well as composite fiber with carbon nano tubes distributed in a nickel matrix or composite fiber of nanoscale nickel and carbon nano tube combined structure. The composite fiber is prepared by depositing nickel on the carbon nano tube fiber by an electrochemical process by taking functional carbon nano tube fiber as a matrix. The nickel accounts for 10-99% by weight, and the size of the nickel grains is 40-300nm. The functional carbon nano tube fiber is carbon nano tube fiber with oxygen-containing functional groups on the surface. The nickel and carbon nano tube composite fiber provided by the invention realizes good interface combination as well as the properties such as high conductivity, high strength and the like, and can be applied to the fields of aerospace, electronics, energy and intelligent spinning as a conductive material, a heat conducting material, a sensor and the like.
Description
Technical field
The present invention relates to complex fiber material of a kind of nickel and CNT and preparation method thereof, be specifically related to the nickel of the high heat conduction of the high conduction of a kind of high-strength light and nano-composite fiber of CNT formation and preparation method thereof, belong to field of nanometer material technology.
Background technology
Carbon nano-tube fibre is the macroscopic fibres material consisting of nano level CNT.Carbon nano-tube fibre integrates the high heat conduction of high strength and high conductivity and the multifunctionality of CNT, has flexibility, can weave, and can be used for developing high-performance composite materials, conductive heat conducting material and flexible electronic, photoelectric material and device, braiding energy storage material.
Carbon nano-tube fibre can be prepared by chemical vapour deposition technique, solution spinning and array spin processes.Especially chemical vapour deposition technique can a step be prepared continuous carbon nano-tube fibre, has the development prospect of industrialization.In the carbon nano-tube fibre of preparing by the method, CNT is that network connects, and controls the fiber of the various carbon nano tube structures that can prepare single wall and double-walled and many walls or these mixing by reaction, is applied to different field.
Nickel has the physical properties such as high conduction, high heat conduction, and excellent mechanics and the physical and chemical performance such as high ductibility, by the compound one-dimensional nano structure of CNT that utilizes of itself and carbon nano-tube fibre, the excellent physicochemical characteristics of excellent mechanical property, electric conductivity thermal conductivity and multifunctionality and nickel, composite and flexible electronic, photoelectric material and the device of the excellent properties such as development is flexible, can weave, high-strength, high conduction, high heat conduction, weave energy storage material.
Nickel prepared by the present invention and the composite fibre of CNT are the nano-composite fiber that nickel and CNT form, and have CNT and are distributed in Ni substrate or the structure of nano level nickel and the coaxial combination of CNT.This composite fibre is to take the carbon nano-tube fibre of functionalization to prepare as matrix adopting electrochemical process is deposited on carbon nano-tube fibre by nickel.CNT in this composite fibre has orientation and is distributed in metal and forms strong interface with metal is combined, can be used as conductive material, Heat Conduction Material, flexible electronic, photoelectric material and device, braiding energy storage material etc. are for space flight and aviation, electronics, the energy and intelligent field of textiles.
Nickel prepared by the present invention and the effect of carbon nano tube composite fibre are different from existing invention.China Patent No. CN201010268622.4 discloses a kind of cable of carbon nano-tube fibre of the surface cladded with nickel coating of preparing.
Summary of the invention
The object of the present invention is to provide a kind of nickel and carbon nano tube composite fibre material and preparation method thereof.Nickel prepared by the present invention and the composite fibre of CNT are the nano-composite fibers that nickel and CNT form, and have the structure that CNT is distributed in Ni substrate or nano level nickel is combined with CNT.This composite fibre is to take the carbon nano-tube fibre of functionalization to make as matrix adopting electrochemical process is deposited on carbon nano-tube fibre by nickel, can be used as conductive material, Heat Conduction Material, flexible electronic, photoelectric material and device, braiding energy storage material etc. are for space flight and aviation, electronics, the energy and intelligent field of textiles.
The complex fiber material of a kind of nickel provided by the invention and CNT is the nano-composite fiber that the carbon nano-tube fibre of nickel and functionalization forms, and is to have CNT to be distributed in Ni substrate or the composite fibre of nano level nickel and the structure of the coaxial combination of CNT.The percentage by weight of nickel is 10 ~ 99 %, and nickel crystallite yardstick is between 40 nanometer ~ 300 nanometers.The carbon nano-tube fibre of described functionalization is the surperficial carbon nano-tube fibre that has oxygen-containing functional group.
CNT in described carbon nano-tube fibre is Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes or their mixture.
The step that a kind of method of preparing nickel and carbon nano tube composite fibre material provided by the invention comprises:
1) by acid treatment 0.5～5 hour for carbon nano-tube fibre, temperature room temperature～100 ° C, makes CNT produce more oxy radical, with practical functionization, processes and obtains functionalized carbon nano-tube fiber;
2) carbon nano-tube fibre of step 1) or the carbon nano-tube fibre that directly generated by chemical vapour deposition technique are dipped in soluble nickel salting liquid, 10～60 ° of C of temperature, apply curtage in carbon nano-tube fibre 1 minute～10 hours.
Described acid comprises the acid of the oxidisability such as nitric acid, sulfuric acid.
The carbon nano-tube fibre of described functionalization is the carbon nano-tube fibre with oxygen-containing functional group, and oxygen-containing functional group mainly comprises hydroxyl (OH), carboxyl (COO) and carbonyl (C=O) etc.
The described current range applying is 0.1～2 A, and the voltage range applying is 0.1～10 V.
In described nickel salt solution, nickel ion concentration is 0.1～2 mole every liter, adds the acid such as boric acid, sulfuric acid for regulator solution pH value.
The technology of the present invention prepare the composite fibre of nickel and CNT can Development of Novel lightweight cable for electric power transfer, electronic fabric, the contour performance composite of conductive and heat-conductive suction ripple, drug delivery carrier and the sensor electronic devices such as electromagnetic shielding, intelligence weaving.
Nickel prepared by the present invention and carbon nano tube composite fibre are the nano-composite fiber that nickel and CNT form.The nickel of preparing by technical solution of the present invention and carbon nano tube composite fibre are that CNT is distributed in Ni substrate or the composite fibre of nano level nickel and the coaxial combination of CNT.In this composite fibre, nickel has good interface with the carbon nano-tube fibre of functionalization by surface action and is combined, and has the performances such as the high heat conduction of high strength and high conductivity simultaneously.
Accompanying drawing explanation
Fig. 1 is the nickel that makes of example 1 of the present invention and the pictorial diagram of carbon nano tube composite fibre.
Fig. 2 is the low power scanning electron microscope (SEM) photograph of example 1 of the present invention nickel used and carbon nano tube composite fibre stretching fracture.
Fig. 3 is the nickel that makes of example 1 of the present invention and the high power scanning electron microscope (SEM) photograph of carbon nano tube composite fibre stretching fracture.
Fig. 4 is the XPS collection of illustrative plates of the C1s of the carbon nano-tube fibre that adopts of example of the present invention 1.
Fig. 5 is the XPS collection of illustrative plates of the C1s of the carbon nano-tube fibre that adopts of example of the present invention 2.
Fig. 6 is the nickel that makes of example 2 of the present invention and the high power scanning electron microscope (SEM) photograph on carbon nano tube composite fibre surface.
Fig. 7 is the nickel that makes of example 3 of the present invention and the high power scanning electron microscope (SEM) photograph on carbon nano tube composite fibre surface.
The specific embodiment
The present invention is described in detail in conjunction with specific embodiments.The experimental technique of unreceipted actual conditions in embodiment, conventionally according to the condition described in normal condition and handbook, or the condition of advising according to manufacturer's description.
Embodiment 1: according to the method for publication number CN101665997A report, prepare carbon nano-tube fibre.Get carbon nano-tube fibre and put into 100
oin the salpeter solution of C, process 5 hours, distilled water is cleaned, put into 1 liter of pre-configured every mol sulfuric acid nickel, 0.2 liter of every mole of nickel chloride and 0.5 liter every mole boric acid mixed aqueous solution, adopt three electrode depositions, carbon nano-tube fibre is as working electrode, Ag/AgCl is as reference electrode, nickel is to electrode, for making deposition process stable, to be placed in 20 ° of C water-baths with whole precipitation equipment and deposit, 1 millivolt of sweep speed setting deposition is per second, sedimentation time 20 minutes, under 3 volts of effects of alternating voltage, prepare nickel and carbon nano tube composite fibre material.Quality before and after the fiber laydown of weighing, the nickel mass percent of composite fibre is about 99 %.Fig. 1 is the pictorial diagram of nickel and carbon nano tube composite fibre.Fig. 2 and Fig. 3 are respectively the nickel that makes and low power and the high power scanning electron microscope (SEM) photograph of carbon nano tube composite fibre fracture.Visible composite fibre is solid, and nickel is full of whole cross section, and has the nickel of granule-morphology and the composite construction of the coaxial combination of CNT, and the diameter of particle is 300 nanometers.Adopt the functional group of the existence of the carbon nano-tube fibre after x-ray photoelectron spectroscopy analyzing and processing.Fig. 4 is the XPS collection of illustrative plates of C1s of the carbon nano-tube fibre of functionalization.From visible this carbon nano-tube fibre of this collection of illustrative plates, there is more carbon-oxygen functional group, mainly comprise C-OH, C=O and COOH, also contain a small amount of O-COO key.These functional groups can make solution and carbon nano-tube fibre infiltrate and can be used as saltation point to make nickel forming core growth thereon, make nickel and CNT have good associativity.
The complex fiber material of this nickel and CNT shows high conductivity, electrical conductivity 0.8 * 10
7every meter of Siemens, compared with fibrillation (3.0 * 10
3every meter of Siemens) improve approximately three orders of magnitude.Composite fibre shows high strength, and intensity is 346 MPas, compared with fibrillation (3.8 MPa) obviously improved ~ 90 times.
Embodiment 2: according to the method for patent CN101665997A report, prepare carbon nano-tube fibre.Get carbon nano-tube fibre and directly put into 1 liter of pre-configured every mol sulfuric acid nickel, 0.2 liter of every mole of nickel chloride and 0.5 liter every mole boric acid mixed aqueous solution, adopt three electrode depositions, carbon nano-tube fibre is as working electrode, Ag/AgCl is as reference electrode, nickel is to electrode, for making deposition process stable, to be placed in 20 ° of C water-baths with whole precipitation equipment deposits, 1 millivolt of sweep speed setting deposition is per second, sedimentation time 20 minutes, under 3 volts of effects of alternating voltage, prepare nickel and carbon nano tube composite fibre.Quality before and after the fiber laydown of weighing, the nickel mass percent of composite fibre is about 96 %.Fig. 6 is respectively nickel that the present invention makes and the high power scanning electron microscope (SEM) photograph of carbon nano tube composite fibre fracture.The outer nickel dam of scanning electron microscopic observation composite fibre fracture is thick ~ and 10 microns, inside is still former carbon nano-tube bundle.The visible CNT of amplifying observation nickel dam is distributed in and in Ni substrate, forms coaxial composite construction.Adopt the functional group of the existence of x-ray photoelectron spectroscopy analysis for carbon nanotubes fiber.Fig. 5 is the XPS collection of illustrative plates of the C1s of carbon nano-tube fibre.From visible this carbon nano-tube fibre of this collection of illustrative plates, there is a small amount of carbon-oxygen functional group, comprise C-OH, C=O and COOH.With comparing containing more multi-functional carbon nano-tube fibre in embodiment 1, further proved that oxygen-containing functional group can play with solution impregnation and can be used as the saltation point forming core growth thereon of nickel.
Embodiment 3: adopt the technology of the present invention, experimentation and condition are with embodiment 1, and changing sedimentation time is 10 minutes, prepares nickel and carbon nano tube composite fibre, quality before and after the fiber laydown of weighing, and the nickel mass percent of composite fibre is about 76 %.Fig. 7 is the nickel that makes of the present invention and the high power scanning electron microscope (SEM) photograph on carbon nano tube composite fibre surface.This composite fibre of scanning electron microscopic observation has the nickel of nano-scale particle pattern and the composite construction of the coaxial combination of CNT, and the diameter of the smallest particles of nickel is 40 nanometers, and the diameter of the largest particles is 160 nanometers.
Embodiment 4: adopt the technology of the present invention, experimentation and condition are with embodiment 1, the functionalization method that changes carbon nano-tube fibre is flooded 10 hours for carbon nano-tube fibre is put under concentrated sulfuric acid room temperature, and changing depositing temperature is 60 ° of C, prepares nickel and carbon nano tube composite fibre.Prepare nickel and carbon nano tube composite fibre.Quality before and after the fiber laydown of weighing, the nickel mass percent of composite fibre is about 99 %.
Embodiment 5: adopt the technology of the present invention, experimentation and condition are with embodiment 1, changing soluble nickel salting liquid is 0.08 mole of every liter of nickelous sulfate, 0.02 mole of every liter of nickel chloride and 0.04 mole of every liter of boric acid, changing depositional mode is the constant voltage of 0.1 V, other preparation process, with example 1, are prepared nickel and carbon nano tube composite fibre.
Embodiment 6: adopt the technology of the present invention, experimentation and condition are with embodiment 1, and changing depositing temperature is 10
oc, sedimentation time 1 minute, making depositional mode into is 0.1 peace constant current, prepares nickel and carbon nano tube composite fibre.Quality before and after the fiber laydown of weighing, the nickel mass percent of composite fibre is about 10 %.
Embodiment 7: adopt the technology of the present invention, experimentation and condition are with embodiment 1, changing soluble nickel salting liquid is 1.5 moles of every liter of nickelous sulfates, 0.5 mole of every liter of nickel chloride and 0.5 mole every liter sulfuric acid mixed aqueous solution, changing depositional mode is the constant current of 2 peaces, prepares nickel and carbon nano tube composite fibre.
Below only in explanation technological invention of the present invention, protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, within all dropping on rights protection scope of the present invention.
Claims (7)
1. the complex fiber material of a nickel and CNT, it is characterized in that this composite fibre is the nano-composite fiber of the carbon nano-tube fibre formation of nickel and functionalization, be have CNT be distributed in Ni substrate or nano level nickel and CNT with the composite fibre of spindle combine structure, the percentage by weight of nickel is 10 ~ 99 %, nickel crystallite yardstick is between 40 nanometer ~ 300 nanometers, and the carbon nano-tube fibre of described functionalization is the surperficial carbon nano-tube fibre that has oxygen-containing functional group.
2. the complex fiber material of nickel according to claim 1 and CNT, is characterized in that the CNT in described carbon nano-tube fibre is Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes or their mixture.
3. a method of preparing nickel claimed in claim 1 and carbon nano tube composite fibre material, is characterized in that the step comprising:
1) at ° C temperature of room temperature～100, by acid dip 0.5～5 hour for carbon nano-tube fibre, make CNT produce more oxy radical, practical functionization is processed, and obtains functionalized carbon nano-tube fiber;
2) carbon nano-tube fibre of step 1) or the carbon nano-tube fibre that directly generated by chemical vapour deposition technique are dipped in soluble nickel salting liquid, 10～60 ° of C of temperature, apply curtage in carbon nano-tube fibre 1 minute～10 hours.
4. method according to claim 3, is characterized in that described acid comprises nitric acid, sulfuric acid.
5. method according to claim 3, is characterized in that the described current range applying is 0.1～2 A, and the voltage range applying is 0.1～10 V.
6. method according to claim 3, is characterized in that in described nickel salt solution, nickel ion concentration is 0.1～2 mole every liter, adds boric acid, sulfuric acid for regulator solution pH value.
7. a method for nickel and carbon nano tube composite fibre material, is characterized in that the step comprising:
1) according to the method for publication number CN101665997A report, prepare carbon nano-tube fibre;
2) carbon nano-tube fibre described in step 1) is put into 100
oin the salpeter solution of C, process 5 hours;
3) by step 2) carbon nano-tube fibre handled well puts into 0.1 liter of pre-configured every mol sulfuric acid nickel, 0.2 liter of every mole of nickel chloride and 0.5 liter every mole boric acid mixed aqueous solution, 20 ° of C deposit, 1 millivolt of sweep speed setting deposition is per second, sedimentation time 20 minutes, under 3 volts of effects of alternating voltage, prepare nickel and carbon nano tube composite fibre material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103882684A (en) * | 2014-04-12 | 2014-06-25 | 哈尔滨工业大学 | Preparation method for magnetic carbon fibers with good interface property |
| CN104726924A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Nickel-tungsten multi-walled carbon nanotube (MWCNT) composite plating solution, plated film and preparation method thereof |
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|---|---|---|---|---|
| CN101255591A (en) * | 2008-04-03 | 2008-09-03 | 厦门大学 | Method for preparing carbon nano-tube/nano-nickel composite film |
| CN101665997A (en) * | 2009-09-25 | 2010-03-10 | 天津大学 | Lamellar carbon nanofibre and preparation method thereof |
| CN101723350A (en) * | 2008-10-29 | 2010-06-09 | 苏州纳米技术与纳米仿生研究所 | Surface modifying method of carbon nanotube fibers |
| CN102561007A (en) * | 2011-12-14 | 2012-07-11 | 天津大学 | Metal oxide and CNT(carbon nano-tube) composite fibre as well as preparation method thereof |
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2013
- 2013-12-05 CN CN201310645142.9A patent/CN103696243B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255591A (en) * | 2008-04-03 | 2008-09-03 | 厦门大学 | Method for preparing carbon nano-tube/nano-nickel composite film |
| CN101723350A (en) * | 2008-10-29 | 2010-06-09 | 苏州纳米技术与纳米仿生研究所 | Surface modifying method of carbon nanotube fibers |
| CN101665997A (en) * | 2009-09-25 | 2010-03-10 | 天津大学 | Lamellar carbon nanofibre and preparation method thereof |
| CN102561007A (en) * | 2011-12-14 | 2012-07-11 | 天津大学 | Metal oxide and CNT(carbon nano-tube) composite fibre as well as preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103882684A (en) * | 2014-04-12 | 2014-06-25 | 哈尔滨工业大学 | Preparation method for magnetic carbon fibers with good interface property |
| CN104726924A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Nickel-tungsten multi-walled carbon nanotube (MWCNT) composite plating solution, plated film and preparation method thereof |
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