CN110482528B - Preparation method of carbon nanotube/ferroferric oxide composite sponge with negative giant magnetoresistance performance - Google Patents

Preparation method of carbon nanotube/ferroferric oxide composite sponge with negative giant magnetoresistance performance Download PDF

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CN110482528B
CN110482528B CN201910785921.6A CN201910785921A CN110482528B CN 110482528 B CN110482528 B CN 110482528B CN 201910785921 A CN201910785921 A CN 201910785921A CN 110482528 B CN110482528 B CN 110482528B
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carbon nanotube
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彭庆宇
陈强
赫晓东
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Harbin Institute of Technology
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Abstract

The invention discloses a preparation method of a carbon nano tube/ferroferric oxide composite sponge with negative giant magnetoresistance performance, which comprises the following steps: step one, preparing a carbon nano tube precursor solution; step two, preparing carbon nanotube sponge; step three, preparing Fe3O4Precursor solution; step four, carbon nano tube/Fe3O4Preparing the composite sponge; step five, carbon nano tube/Fe3O4Washing the composite sponge graphene belt with sponge; step six, carbon nano tube/Fe3O4And (5) drying the composite sponge. The invention adopts a chemical vapor deposition method to prepare the carbon nano tube sponge, and Fe grows in the carbon nano tube sponge by a polyol method by virtue of a three-dimensional porous network structure3O4Nano granular rice and then preparing carbon nano tube/Fe with negative giant magnetoresistance3O4A composite sponge. The invention can keep the light and high conductivity of carbon nanometer tube sponge, and improve the giant magnetic resistance.

Description

Preparation method of carbon nanotube/ferroferric oxide composite sponge with negative giant magnetoresistance performance
Technical Field
The invention belongs to the technical field of material science, and relates to a carbon nano tube/Fe with negative giant magnetoresistance3O4A preparation method of a composite sponge.
Background
In 2007, the nobel physics awards to albe-felt (Dr. Fert), a french scientist, and peter-guillain-berg (Dr. Gr ü nberg), a german scientist, rewarding their contributions in the discovery and development of giant magnetoresistance phenomena. Since then, giant magnetoresistive based electronics have been developed and widely used in various fields, in which the local magnetoresistance effect of materials is utilized to develop a new class of magnetoresistive sensors, Giant Magnetoresistive (GMR) sensors. Compared with the traditional magnetoresistive sensor, the giant magnetoresistive sensor has the advantages of high sensitivity, good reliability, wide measurement range, severe environment resistance, small volume and the like, and has wide application prospect.
Although the giant magnetoresistance effect was originally found in multilayer metal structures, it is difficult to achieve coherent spin transport on the nanometer scale in metal and inorganic semiconductors. Spin transport refers primarily to the transport of electron spins in metals and semiconductors. Therefore, there is an urgent need to develop new materials to realize effective spin injection and spin transport, and to provide possibility for further improving the sensitivity of the magnetoresistive sensor. In recent years, physicists and chemists have attempted to select organic materials as new spin transport materials because carbon elements have weak spin-orbit coupling and hyperfine interactions, which allow carbon elements to have relatively long spin relaxation times (also known as spin lattice times). Carbon materials (carbon nanotubes and graphene) and organic semiconductor materials have the characteristics of light weight, simple production process, low cost, chemical stability, biocompatibility and the like, and thus, the carbon materials and the organic semiconductor materials attract extensive attention of students. However, if the carbon material and the organic semiconductor material are applied to the giant magnetoresistance sensor, a problem of insufficient conductivity is faced.
The carbon nanotube sponge is used as a three-dimensional macroscopic porous material of the carbon nanotube, and multi-wall carbon nanotubes grown by a chemical vapor deposition method are lapped together in an intricate disorder manner to be self-assembled into a three-dimensional porous network structure, so that the carbon nanotube sponge has excellent conductivity and the resistivity of about 6.08 multiplied by 10-1Omega cm. In addition, the carbon nanotube sponge is light (5-25 mg/cm)3) And the deformation is large (the strain amount is up to 95 percent), and the three-dimensional porous skeleton structure is characterized. Meanwhile, some magnetic particles such as ferromagnetic Fe can be loaded by virtue of the skeleton structure in the carbon nanotube sponge3O4The nano particles can further improve the giant magnetoresistance performance of the carbon nano tube sponge, and can greatly improve the sensitivity of the sensor when being applied to the giant magnetoresistance sensor.
In summary, carbon nanotube/Fe was prepared3O4The composite sponge keeps the light weight and high conductivity of the carbon nanotube sponge, and greatly improves the giant magnetoresistance performance of the carbon nanotube sponge.
Disclosure of Invention
In order to solve the problems that the existing material used as a giant magnetoresistance sensor is mostly powder, can not be directly used and has poor conductivity, the invention provides a carbon nano tube/Fe with negative giant magnetoresistance performance3O4A preparation method of a composite sponge. The invention can keep the light and high conductivity of carbon nanometer tube sponge, and improve the giant magnetic resistance.
The purpose of the invention is realized by the following technical scheme:
carbon nano tube/Fe with negative giant magnetoresistance performance3O4The preparation method of the composite sponge comprises the following steps:
step one, preparing a carbon nano tube precursor solution:
dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene, shaking up by hand, putting into an ultrasonic machine for ultrasonic dispersion, and ensuring that the catalyst is fully dissolved in a carbon source solution to obtain a carbon nano tube precursor solution, wherein: the frequency of the ultrasonic machine is 10-80 KHz, the ultrasonic dispersion time is 2-4 h, and the mass-to-volume ratio of ferrocene to 1, 2-dichlorobenzene is 6g:100 ml;
step two, preparing the carbon nano tube sponge:
preparing the carbon nano tube sponge with a three-dimensional network structure by adopting a chemical vapor deposition method, namely: the method adopts two-stage heating of a preheating zone and a reaction zone to realize catalytic cracking of a carbon source so as to form the carbon nanotube sponge, and comprises the following specific steps: injecting the precursor solution of the carbon nano tube into a preheating zone of a tube furnace for vaporization in H2And carrying a carbon source and a catalyst into a reaction zone of the tubular furnace to react under the drive of the Ar mixed gas to form carbon nanotube sponge, wherein: the temperature of the preheating zone is 200 ℃, and the temperature of the reaction zone is 865 ℃; h2And Ar mixed gas, H230% by volume, H2The flow rate of the mixed gas of Ar and Ar is 1.6L/min; the injection rate of the precursor solution is 0.25 ml/min;
step three, preparing Fe3O4Precursor solution:
adding iron acetylacetonate powder into triethylene glycol solution, mixing, magnetically stirring, and performing ultrasonic treatment to obtain uniform and stable Fe3O4A red-orange solution, wherein: the mass volume ratio of the ferric acetylacetonate to the triethylene glycol solution is 0.10-0.60 g:20 ml;
step four, carbon nano tube/Fe3O4Preparing the composite sponge:
method for growing Fe in carbon nanotube sponge by adopting polyalcohol3O4Nanoparticles, preparation of carbon nanotubes/Fe3O4The composite sponge comprises the following specific steps: cutting carbon nanotube sponge into 100mg pieces, and adding Fe3O4Continuing to perform ultrasonic treatment in the reddish orange solution, vacuumizing to discharge air in the sponge, and ensuring that the inner pores of the carbon nanotube sponge are completely filled with the solution; transferring the uniform solution after ultrasonic treatment and the carbon nanotube sponge filled with the solution into a three-neck flask under the protection of nitrogenHeating until the solution boils, condensing and refluxing, and stopping heating, wherein: the ultrasonic time is 4-8 h, and the ultrasonic frequency is 10-80 KHz; the vacuum degree of the vacuum pumping is-0.1-0.3 Mpa, and the heating rate is 1-3 ℃/min; the time of condensation and reflux is 30-60 min;
step five, carbon nano tube/Fe3O4Washing the composite sponge graphene with the sponge:
pouring off black liquid obtained by the reaction, repeatedly soaking and washing the sponge by using ethyl acetate, absolute ethyl alcohol and deionized water respectively until washing residual liquid is zero, removing unreacted solvent and reaction byproducts, and finally completely filling the sponge with deionized water, wherein: the washing sponge is carried out according to the following steps: firstly, putting the reacted sponge into 30ml of ethyl acetate for soaking for 4 hours, and removing most of unreacted solvent and reaction byproducts; then, pouring the liquid, adding the liquid into 50ml of absolute ethyl alcohol, stirring the liquid for 20min by using a glass rod, pouring the liquid, adding 50ml of absolute ethyl alcohol, stirring the liquid by using the glass rod, and repeatedly washing the liquid by using the absolute ethyl alcohol until the liquid is colorless until no colored liquid flows out of the sponge; finally, pouring out the liquid, adding 100ml of deionized water, and standing for 12 h;
step six, carbon nano tube/Fe3O4Drying the composite sponge:
carbon nanotubes/Fe frozen with liquid nitrogen3O4Compounding the sponge, and then transferring the sponge to a freeze dryer for drying for 12-36 h to obtain dry carbon nano tube/Fe3O4Compounding sponge;
step seven, carbon nano tube/Fe3O4Preparing a composite sponge giant magnetoresistance sensor:
drying the carbon nano tube/Fe3O4The composite sponge is cut to obtain the required size, such as 1cm multiplied by 2mm, and the giant magnetoresistance performance test is carried out, and the giant magnetoresistance sensor can be directly used as the giant magnetoresistance sensor.
Compared with the prior art, the invention has the following advantages:
1. the carbon nanotube sponge has excellent conductivity and resistivity of about 6.08 × 10-1Omega cm. Except thatBesides, the carbon nanotube sponge is light (5-25 mg/cm)3) The deformation amount is large (the strain amount is up to 95 percent), and the three-dimensional porous framework structure has the characteristics of three-dimensional porous framework structure. Meanwhile, magnetic Fe is loaded by virtue of a skeleton structure in the carbon nano tube sponge3O4The nano particles can further improve the giant magnetoresistance performance of the carbon nano tube sponge, and can greatly improve the sensitivity of the sensor when being applied to the giant magnetoresistance sensor.
2. The invention adopts a chemical vapor deposition method to prepare the carbon nano tube sponge, and Fe grows in the carbon nano tube sponge by a polyol method by virtue of a three-dimensional porous network structure3O4Nano granular rice and then preparing carbon nano tube/Fe with negative giant magnetoresistance3O4A composite sponge. By regulating and controlling the proportion of acetylacetone paste and triethylene glycol, carbon nano tube/Fe with different ferroferric oxide load rates is obtained3O4A composite sponge. Fe3O4The load rate reaches 28%, 31%, 35% and 51% in sequence, and the giant magnetoresistance performance is reduced from-1.6% to-1.7%, from-2.1%, from-2.3% to-2.5%.
Drawings
FIG. 1 shows the carbon nanotube sponge and carbon nanotube/Fe obtained in the second and sixth steps of example 13O4A topography of the composite sponge;
FIG. 2 shows the carbon nanotubes/Fe obtained in step six of examples 1 to 43O4A microscopic topography of the composite sponge;
FIG. 3 shows the carbon nanotubes/Fe obtained in step six of examples 1 to 43O4Thermogravimetric curves of composite sponges;
FIG. 4 shows the carbon nanotubes/Fe obtained in step six of examples 1 to 43O4A histogram of resistivity of the composite sponge;
FIG. 5 shows the carbon nanotubes/Fe obtained in step six of examples 1 to 43O4Giant magnetoresistance property curve of composite sponge.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1:
in this example, carbon nanotube/Fe 3O with negative giant magnetoresistance4The preparation method of the composite sponge is realized according to the following steps:
step one, preparing a carbon nano tube precursor solution:
dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene, uniformly shaking by hand, putting the liquid carbon source into an ultrasonic machine with the frequency of 80KHz for ultrasonic dispersion for 2 hours, and ensuring that the catalyst is fully dissolved in a carbon source solution to obtain a carbon nano tube precursor solution, wherein: the mass volume ratio of the ferrocene to the 1, 2-dichlorobenzene is 6g:100 ml.
Step two, preparing the carbon nano tube sponge:
preparing the carbon nano tube sponge with a three-dimensional network structure by adopting a chemical vapor deposition method, namely: the method adopts two-stage heating of a preheating zone and a reaction zone to realize catalytic cracking of a carbon source so as to form the carbon nanotube sponge, and comprises the following specific steps: under the protection of argon, the preheating zone was heated to 200 ℃ and the reaction zone was heated to 865 ℃ at a rate of 10 ℃/min. And (3) closing an argon switch, opening a hydrogen-argon mixed gas with the hydrogen content accounting for 30%, and setting the flow at 1.6L/min. And (3) sucking 30ml of reaction solution by using a disposable syringe, and injecting the carbon nano tube precursor solution prepared in the step one into the preheating zone by using a precision injection pump at 0.25 ml/min. The carbon nanotube precursor solution is rapidly vaporized in H2And carrying the carbon source and the catalyst into a reaction zone of the tubular furnace under the drive of the Ar mixed gas to carry out cracking, growth and stacking reaction to form the carbon nanotube sponge.
Step three, preparing Fe3O4Precursor solution:
adding iron acetylacetonate powder into triethylene glycol solution, mixing, magnetically stirring, and performing ultrasonic treatment to obtain uniform and stable Fe3O4A red-orange solution, wherein: the mass-volume ratio of the ferric acetylacetonate to the triethylene glycol solution is 0.10g to 20 ml.
Step four, carbon nano tube/Fe3O4Preparation of composite spongePreparing:
method for growing Fe in carbon nanotube sponge by adopting polyalcohol3O4Nanoparticles, preparation of carbon nanotubes/Fe3O4The composite sponge comprises the following specific steps: cutting carbon nanotube sponge into 100mg pieces, and adding Fe3O4Continuing to perform ultrasonic treatment in the reddish orange solution for 4 hours at the ultrasonic frequency of 80KHz, vacuumizing to discharge air in the sponge, and ensuring that the pores in the carbon nanotube sponge are completely filled with the solution; transferring the uniform solution after the ultrasonic treatment and the carbon nanotube sponge filled with the solution into a three-neck flask, heating the solution to boil under the protection of nitrogen, condensing and refluxing, and stopping heating, wherein: the vacuum degree of the vacuum pumping is 0.2Mpa, and the heating rate is 3 ℃/min; the time of condensing reflux was 30 min.
Step five, carbon nano tube/Fe3O4Washing the composite sponge graphene with the sponge:
pouring off black liquid obtained by the reaction, repeatedly soaking and washing the sponge by using ethyl acetate, absolute ethyl alcohol and deionized water respectively until washing residual liquid is zero, removing unreacted solvent and reaction byproducts, and finally completely filling the sponge with deionized water, wherein: the washing sponge is carried out according to the following steps: firstly, putting the reacted sponge into 30ml of ethyl acetate for soaking for 4 hours, and removing most of unreacted solvent and reaction byproducts; then, pouring the liquid, adding the liquid into 50ml of absolute ethyl alcohol, stirring the liquid for 20min by using a glass rod, pouring the liquid, adding 50ml of absolute ethyl alcohol, stirring the liquid by using the glass rod, and repeatedly washing the liquid by using the absolute ethyl alcohol until the liquid is colorless until no colored liquid flows out of the sponge; finally, the liquid was decanted, 100ml of deionized water was added, and the mixture was left for 12 hours.
Step six, carbon nano tube/Fe3O4Drying the composite sponge:
carbon nanotubes/Fe frozen with liquid nitrogen3O4Compounding sponge, and transferring to a freeze dryer for drying for 24h to obtain dried carbon nanotube/Fe3O4A composite sponge.
Step seven, carbon nano tube/Fe3O4Preparing a composite sponge giant magnetoresistance sensor:
drying the carbon nano tube/Fe3O4The composite sponge is cut to obtain the required size, such as 1cm multiplied by 2mm, and the giant magnetoresistance performance test is carried out, and the giant magnetoresistance sensor can be directly used as the giant magnetoresistance sensor.
Carbon nanotubes/Fe obtained in this example3O4In the composite sponge, Fe3O4The loading rate of the sponge is 28 percent, the sponge has the resistivity of 4.12ohm.cm and the giant magnetoresistance of-1.7 percent, and is improved by 6.3 percent compared with the pure carbon nanotube sponge.
Example 2:
in this embodiment, the method for preparing the carbon nanotube/Fe 3O4 composite sponge with negative giant magnetoresistance performance is implemented according to the following steps:
step one, preparing a carbon nano tube precursor solution:
dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene, uniformly shaking by hand, putting the liquid carbon source into an ultrasonic machine with the frequency of 80KHz for ultrasonic dispersion for 2 hours, and ensuring that the catalyst is fully dissolved in a carbon source solution to obtain a carbon nano tube precursor solution, wherein: the mass volume ratio of the ferrocene to the 1, 2-dichlorobenzene is 6g:100 ml.
Step two, preparing the carbon nano tube sponge:
preparing the carbon nano tube sponge with a three-dimensional network structure by adopting a chemical vapor deposition method, namely: the method adopts two-stage heating of a preheating zone and a reaction zone to realize catalytic cracking of a carbon source so as to form the carbon nanotube sponge, and comprises the following specific steps: under the protection of argon, the preheating zone was heated to 200 ℃ and the reaction zone was heated to 865 ℃ at a rate of 10 ℃/min. And (3) closing an argon switch, opening a hydrogen-argon mixed gas with the hydrogen content accounting for 30%, and setting the flow at 1.6L/min. And (3) sucking 30ml of reaction solution by using a disposable syringe, and injecting the carbon nano tube precursor solution prepared in the step one into the preheating zone by using a precision injection pump at 0.25 ml/min. The carbon nanotube precursor solution is rapidly vaporized in H2And carrying the carbon source and the catalyst into a reaction zone of the tubular furnace under the drive of the Ar mixed gas to carry out cracking, growth and stacking reaction to form the carbon nanotube sponge.
Step three, preparing Fe3O4Precursor solution:
adding iron acetylacetonate powder into triethylene glycol solution, mixing, magnetically stirring, and performing ultrasonic treatment to obtain uniform and stable Fe3O4A red-orange solution, wherein: the mass-volume ratio of the ferric acetylacetonate to the triethylene glycol solution is 0.20g to 20 ml.
Step four, carbon nano tube/Fe3O4Preparing the composite sponge:
method for growing Fe in carbon nanotube sponge by adopting polyalcohol3O4Nanoparticles, preparation of carbon nanotubes/Fe3O4The composite sponge comprises the following specific steps: cutting carbon nanotube sponge into 100mg pieces, and adding Fe3O4Continuing to perform ultrasonic treatment in the reddish orange solution for 4 hours at the ultrasonic frequency of 80KHz, vacuumizing to discharge air in the sponge, and ensuring that the pores in the carbon nanotube sponge are completely filled with the solution; transferring the uniform solution after the ultrasonic treatment and the carbon nanotube sponge filled with the solution into a three-neck flask, heating the solution to boil under the protection of nitrogen, condensing and refluxing, and stopping heating, wherein: the vacuum degree of the vacuum pumping is 0.2Mpa, and the heating rate is 3 ℃/min; the time of condensing reflux was 30 min.
Step five, carbon nano tube/Fe3O4Washing the composite sponge graphene with the sponge:
pouring off black liquid obtained by the reaction, repeatedly soaking and washing the sponge by using ethyl acetate, absolute ethyl alcohol and deionized water respectively until washing residual liquid is zero, removing unreacted solvent and reaction byproducts, and finally completely filling the sponge with deionized water, wherein: the washing sponge is carried out according to the following steps: firstly, putting the reacted sponge into 30ml of ethyl acetate for soaking for 4 hours, and removing most of unreacted solvent and reaction byproducts; then, pouring the liquid, adding the liquid into 50ml of absolute ethyl alcohol, stirring the liquid for 20min by using a glass rod, pouring the liquid, adding 50ml of absolute ethyl alcohol, stirring the liquid by using the glass rod, and repeatedly washing the liquid by using the absolute ethyl alcohol until the liquid is colorless until no colored liquid flows out of the sponge; finally, the liquid was decanted, 100ml of deionized water was added, and the mixture was left for 12 hours.
Step six, carbon nano tube/Fe3O4Drying the composite sponge:
carbon nanotubes/Fe frozen with liquid nitrogen3O4Compounding sponge, and transferring to a freeze dryer for drying for 24h to obtain dried carbon nanotube/Fe3O4A composite sponge.
Step seven, carbon nano tube/Fe3O4Preparing a composite sponge giant magnetoresistance sensor:
drying the carbon nano tube/Fe3O4The composite sponge is cut to obtain the required size, such as 1cm multiplied by 2mm, and the giant magnetoresistance performance test is carried out, and the giant magnetoresistance sensor can be directly used as the giant magnetoresistance sensor.
Carbon nanotubes/Fe obtained in this example3O4In the composite sponge, Fe3O4The loading rate of the sponge is 31 percent, the sponge has the resistivity of 6.84ohm.cm and the giant magnetoresistance of-2.1 percent, and is improved by 31.3 percent compared with the pure carbon nanotube sponge.
Example 3:
in this embodiment, the method for preparing the carbon nanotube/Fe 3O4 composite sponge with negative giant magnetoresistance performance is implemented according to the following steps:
step one, preparing a carbon nano tube precursor solution:
dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene, uniformly shaking by hand, putting the liquid carbon source into an ultrasonic machine with the frequency of 80KHz for ultrasonic dispersion for 2 hours, and ensuring that the catalyst is fully dissolved in a carbon source solution to obtain a carbon nano tube precursor solution, wherein: the mass volume ratio of the ferrocene to the 1, 2-dichlorobenzene is 6g:100 ml.
Step two, preparing the carbon nano tube sponge:
preparing the carbon nano tube sponge with a three-dimensional network structure by adopting a chemical vapor deposition method, namely: the method adopts two-stage heating of a preheating zone and a reaction zone to realize catalytic cracking of a carbon source so as to form the carbon nanotube sponge, and comprises the following specific steps: under the protection of argon, the preheating zone was heated to 200 ℃ and the reaction zone was heated to 865 ℃ at a rate of 10 ℃/min. Closing the argon switch and openingHydrogen-argon mixed gas with the hydrogen content of 30 percent is set to have the flow of 1.6L/min. And (3) sucking 30ml of reaction solution by using a disposable syringe, and injecting the carbon nano tube precursor solution prepared in the step one into the preheating zone by using a precision injection pump at 0.25 ml/min. The carbon nanotube precursor solution is rapidly vaporized in H2And carrying the carbon source and the catalyst into a reaction zone of the tubular furnace under the drive of the Ar mixed gas to carry out cracking, growth and stacking reaction to form the carbon nanotube sponge.
Step three, preparing Fe3O4Precursor solution:
adding iron acetylacetonate powder into triethylene glycol solution, mixing, magnetically stirring, and performing ultrasonic treatment to obtain uniform and stable Fe3O4A red-orange solution, wherein: the mass-volume ratio of the ferric acetylacetonate to the triethylene glycol solution is 0.40g to 20 ml.
Step four, carbon nano tube/Fe3O4Preparing the composite sponge:
method for growing Fe in carbon nanotube sponge by adopting polyalcohol3O4Nanoparticles, preparation of carbon nanotubes/Fe3O4The composite sponge comprises the following specific steps: cutting carbon nanotube sponge into 100mg pieces, and adding Fe3O4Continuing to perform ultrasonic treatment in the reddish orange solution for 4 hours at the ultrasonic frequency of 80KHz, vacuumizing to discharge air in the sponge, and ensuring that the pores in the carbon nanotube sponge are completely filled with the solution; transferring the uniform solution after the ultrasonic treatment and the carbon nanotube sponge filled with the solution into a three-neck flask, heating the solution to boil under the protection of nitrogen, condensing and refluxing, and stopping heating, wherein: the vacuum degree of the vacuum pumping is 0.2Mpa, and the heating rate is 3 ℃/min; the time of condensing reflux was 30 min.
Step five, carbon nano tube/Fe3O4Washing the composite sponge graphene with the sponge:
pouring off black liquid obtained by the reaction, repeatedly soaking and washing the sponge by using ethyl acetate, absolute ethyl alcohol and deionized water respectively until washing residual liquid is zero, removing unreacted solvent and reaction byproducts, and finally completely filling the sponge with deionized water, wherein: the washing sponge is carried out according to the following steps: firstly, putting the reacted sponge into 30ml of ethyl acetate for soaking for 4 hours, and removing most of unreacted solvent and reaction byproducts; then, pouring the liquid, adding the liquid into 50ml of absolute ethyl alcohol, stirring the liquid for 20min by using a glass rod, pouring the liquid, adding 50ml of absolute ethyl alcohol, stirring the liquid by using the glass rod, and repeatedly washing the liquid by using the absolute ethyl alcohol until the liquid is colorless until no colored liquid flows out of the sponge; finally, the liquid was decanted, 100ml of deionized water was added, and the mixture was left for 12 hours.
Step six, carbon nano tube/Fe3O4Drying the composite sponge:
carbon nanotubes/Fe frozen with liquid nitrogen3O4Compounding sponge, and transferring to a freeze dryer for drying for 24h to obtain dried carbon nanotube/Fe3O4A composite sponge.
Step seven, carbon nano tube/Fe3O4Preparing a composite sponge giant magnetoresistance sensor:
drying the carbon nano tube/Fe3O4The composite sponge is cut to obtain the required size, such as 1cm multiplied by 2mm, and the giant magnetoresistance performance test is carried out, and the giant magnetoresistance sensor can be directly used as the giant magnetoresistance sensor.
Carbon nanotubes/Fe obtained in this example3O4In the composite sponge, Fe3O4The loading rate is 35%, the resistivity of the sponge is 7.98ohm.cm, the giant magnetoresistance performance is-2.3%, and the giant magnetoresistance performance is improved by 43.8% compared with pure carbon nanotube sponge.
Example 4:
in this embodiment, the method for preparing the carbon nanotube/Fe 3O4 composite sponge with negative giant magnetoresistance performance is implemented according to the following steps:
step one, preparing a carbon nano tube precursor solution: dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene, uniformly shaking by hand, and putting the liquid carbon source into an ultrasonic machine with the frequency of 80KHz for ultrasonic dispersion for 2 hours to ensure that the catalyst is fully dissolved in a carbon source solution to obtain a carbon nano tube precursor solution. The volume ratio of the ferrocene mass to the 1, 2-dichlorobenzene is 6g:100 ml.
Step two, preparing the carbon nano tube sponge:
preparing the carbon nano tube sponge with a three-dimensional network structure by adopting a chemical vapor deposition method, namely: the method adopts two-stage heating of a preheating zone and a reaction zone to realize catalytic cracking of a carbon source so as to form the carbon nanotube sponge, and comprises the following specific steps: under the protection of argon, the preheating zone was heated to 200 ℃ and the reaction zone was heated to 865 ℃ at a rate of 10 ℃/min. And (3) closing an argon switch, opening a hydrogen-argon mixed gas with the hydrogen content accounting for 30%, and setting the flow at 1.6L/min. And (3) sucking 30ml of reaction solution by using a disposable syringe, and injecting the carbon nano tube precursor solution prepared in the step one into the preheating zone by using a precision injection pump at 0.25 ml/min. The carbon nanotube precursor solution is rapidly vaporized in H2And carrying the carbon source and the catalyst into a reaction zone of the tubular furnace under the drive of the Ar mixed gas to carry out cracking, growth and stacking reaction to form the carbon nanotube sponge.
Step three, preparing Fe3O4Precursor solution:
adding iron acetylacetonate powder into triethylene glycol solution, mixing, magnetically stirring, and performing ultrasonic treatment to obtain uniform and stable Fe3O4A red-orange solution, wherein: the mass-volume ratio of the ferric acetylacetonate to the triethylene glycol solution is 0.60g to 20 ml.
Step four, carbon nano tube/Fe3O4Preparing the composite sponge:
method for growing Fe in carbon nanotube sponge by adopting polyalcohol3O4Nanoparticles, preparation of carbon nanotubes/Fe3O4The composite sponge comprises the following specific steps: cutting carbon nanotube sponge into 100mg pieces, and adding Fe3O4Continuing to perform ultrasonic treatment in the reddish orange solution for 4 hours at the ultrasonic frequency of 80KHz, vacuumizing to discharge air in the sponge, and ensuring that the pores in the carbon nanotube sponge are completely filled with the solution; transferring the uniform solution after the ultrasonic treatment and the carbon nanotube sponge filled with the solution into a three-neck flask, heating the solution to boil under the protection of nitrogen, condensing and refluxing, and stopping heating, wherein: the vacuum degree of the vacuum pumping is 0.2Mpa, and the heating rate is 3 ℃/min; the time of condensing reflux was 30 min.
Step five, carbon nano tube/Fe3O4Washing the composite sponge graphene with the sponge:
pouring off black liquid obtained by the reaction, repeatedly soaking and washing the sponge by using ethyl acetate, absolute ethyl alcohol and deionized water respectively until washing residual liquid is zero, removing unreacted solvent and reaction byproducts, and finally completely filling the sponge with deionized water, wherein: the washing sponge is carried out according to the following steps: firstly, putting the reacted sponge into 30ml of ethyl acetate for soaking for 4 hours, and removing most of unreacted solvent and reaction byproducts; then, pouring the liquid, adding the liquid into 50ml of absolute ethyl alcohol, stirring the liquid for 20min by using a glass rod, pouring the liquid, adding 50ml of absolute ethyl alcohol, stirring the liquid by using the glass rod, and repeatedly washing the liquid by using the absolute ethyl alcohol until the liquid is colorless until no colored liquid flows out of the sponge; finally, the liquid was decanted, 100ml of deionized water was added, and the mixture was left for 12 hours.
Step six, carbon nano tube/Fe3O4Drying the composite sponge:
carbon nanotubes/Fe frozen with liquid nitrogen3O4Compounding sponge, and transferring to a freeze dryer for drying for 24h to obtain dried carbon nanotube/Fe3O4A composite sponge.
Step seven, carbon nano tube/Fe3O4Preparing a composite sponge giant magnetoresistance sensor:
drying the carbon nano tube/Fe3O4The composite sponge is cut to obtain the required size, such as 1cm multiplied by 2mm, and the giant magnetoresistance performance test is carried out, and the giant magnetoresistance sensor can be directly used as the giant magnetoresistance sensor.
Carbon nanotubes/Fe obtained in this example3O4In the composite sponge, Fe3O4The load factor of the sponge is 51 percent, the sponge has the resistivity of 12.68ohm.cm and the giant magnetoresistance of-2.5 percent, and is improved by 56.3 percent compared with the pure carbon nanotube sponge.
FIG. 1 shows, by way of example 1, macroscopic photographs of Fe-supported catalysts3O4The appearance of the composite sponge is not obviously different from that of the pure carbon nanotube sponge.
FIG. 2 is a SEM test of the carbon nanotubes/Fe obtained in step six of examples 1 to 43O4The internal microscopic morphology of the composite sponge shows that the carbon nano-tube is loaded with Fe3O4The gradual increase in particles further demonstrates that examples 1 to 4 successfully produce different Fe3O4A composite sponge with a loading rate.
FIG. 3 quantitative determination of Fe in the composite sponges prepared in examples 1 to 4 by TGA testing3O4Were 28%, 31%, 35%, 51%, respectively, further demonstrating the successful production of Fe in examples 1 to 43O4Composite sponges with progressively higher loading rates.
FIG. 4 shows the electrical resistivity of the composite sponges prepared in examples 1-4 as 4.12 ohm-cm, 6.84 ohm-cm, 7.98 ohm-cm, 12.68 ohm-cm, respectively, demonstrating the behavior with Fe3O4The loading rate increases and the resistivity of the composite sponge also increases.
FIG. 5 quantitatively shows the giant magnetoresistance properties of the composite sponges prepared in examples 1 to 4, by the giant magnetoresistance test, at-1.7%, -2.1%, -2.3%, -2.5%, respectively, under a 9T magnetic field, illustrating the behavior with Fe3O4The load rate is increased, the giant magnetoresistance performance is also improved, and the Fe is proved3O4The load of (2) successfully improves the giant magnetoresistance performance of the composite sponge.

Claims (8)

1. Carbon nano tube/Fe with negative giant magnetoresistance performance3O4The preparation method of the composite sponge is characterized by comprising the following steps:
step one, preparing a carbon nano tube precursor solution:
dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene, uniformly shaking by hand, and putting the liquid carbon source into an ultrasonic machine for ultrasonic dispersion to ensure that the catalyst is fully dissolved in a carbon source solution to obtain a carbon nano tube precursor solution;
step two, preparing the carbon nano tube sponge:
injecting the precursor solution of the carbon nano tube into a preheating zone of a tube furnace for vaporization in H2And Ar mixed gasThe carbon source and the catalyst are brought into a reaction zone of the tubular furnace to react under the drive of the carbon source and the catalyst to form carbon nanotube sponge;
step three, preparing Fe3O4Precursor solution:
adding iron acetylacetonate powder into triethylene glycol solution, mixing, magnetically stirring, and performing ultrasonic treatment to obtain uniform and stable Fe3O4A red-orange solution;
step four, carbon nano tube/Fe3O4Preparing the composite sponge:
method for growing Fe in carbon nanotube sponge by adopting polyalcohol3O4Nanoparticles, preparation of carbon nanotubes/Fe3O4The composite sponge comprises the following specific steps: cutting carbon nanotube sponge into small pieces, and adding Fe3O4Continuing to perform ultrasonic treatment in the reddish orange solution, vacuumizing to discharge air in the sponge, and ensuring that the inner pores of the carbon nanotube sponge are completely filled with the solution; transferring the uniform solution after ultrasonic treatment and the carbon nanotube sponge filled with the solution into a three-neck flask, heating until the solution boils under the protection of nitrogen, condensing and refluxing, and stopping heating;
step five, carbon nano tube/Fe3O4Washing the composite sponge graphene with the sponge:
pouring off black liquid obtained by the reaction, repeatedly soaking and washing the sponge by using ethyl acetate, absolute ethyl alcohol and deionized water respectively until washing residual liquid is free, removing unreacted solvent and reaction byproducts, and finally completely filling the sponge with the deionized water;
step six, carbon nano tube/Fe3O4Drying the composite sponge:
carbon nanotubes/Fe frozen with liquid nitrogen3O4Compounding sponge, and drying in a freeze drier to obtain dried carbon nanotube/Fe3O4A composite sponge.
2. The carbon nanotube/Fe with negative giant magnetoresistance performance of claim 13O4The preparation method of the composite sponge is characterized by comprising the following stepsIn the first step, the frequency of an ultrasonic machine is 10-80 KHz, the ultrasonic dispersion time is 2-4 h, and the mass volume ratio of ferrocene to 1, 2-dichlorobenzene is 6g:100 ml.
3. The carbon nanotube/Fe with negative giant magnetoresistance performance of claim 13O4The preparation method of the composite sponge is characterized in that in the second step, the temperature of a preheating zone is 200 ℃, and the temperature of a reaction zone is 865 ℃; h2And Ar mixed gas, H230% by volume, H2The flow rate of the mixed gas of Ar and Ar is 1.6L/min; the injection rate of the precursor solution was 0.25 ml/min.
4. The carbon nanotube/Fe with negative giant magnetoresistance performance of claim 13O4The preparation method of the composite sponge is characterized in that in the third step, the mass-volume ratio of the ferric acetylacetonate to the triethylene glycol solution is 0.10-0.60 g:20 ml.
5. The carbon nanotube/Fe with negative giant magnetoresistance performance of claim 13O4The preparation method of the composite sponge is characterized in that the ultrasonic time is 4-8 h, and the ultrasonic frequency is 10-80 KHz; the vacuum degree of the vacuum pumping is-0.1-0.3 Mpa, and the heating rate is 1-3 ℃/min; the time of condensation and reflux is 30-60 min.
6. The carbon nanotube/Fe with negative giant magnetoresistance performance of claim 13O4The preparation method of the composite sponge is characterized in that in the fifth step, the sponge washing is carried out according to the following steps: firstly, putting the reacted sponge into 30ml of ethyl acetate for soaking for 4 hours, and removing most of unreacted solvent and reaction byproducts; then, pouring the liquid, adding the liquid into 50ml of absolute ethyl alcohol, stirring the liquid for 20min by using a glass rod, pouring the liquid, adding 50ml of absolute ethyl alcohol, stirring the liquid by using the glass rod, and repeatedly washing the liquid by using the absolute ethyl alcohol until the liquid is colorless until no colored liquid flows out of the sponge; finally, the liquid was decanted, 100ml of deionized water was added, and the mixture was left for 12 hours.
7. The carbon nanotube/Fe with negative giant magnetoresistance performance of claim 13O4The preparation method of the composite sponge is characterized in that in the sixth step, the drying time is 12-36 hours.
8. Carbon nanotubes/Fe prepared by the method of any one of claims 1 to 73O4The application of the composite sponge in giant magnetoresistance sensors.
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