CN106987925B - Functionalized graphene preparation method based on ion exchange - Google Patents
Functionalized graphene preparation method based on ion exchange Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 65
- 238000005342 ion exchange Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000835 fiber Substances 0.000 claims abstract description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000002791 soaking Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 238000002166 wet spinning Methods 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract 2
- 239000002243 precursor Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 230000001112 coagulating effect Effects 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000011149 active material Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009044 synergistic interaction Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003759 clinical diagnosis Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
Abstract
The invention relates to a preparation method of functionalized graphene fibers based on ion exchange; the functionalized graphene fiber is prepared by using graphene oxide as a precursor, performing wet spinning, performing ion exchange with a metal salt solution, and finally performing high-temperature reduction. The preparation method comprises the following steps: preparing graphene oxide fibers by a wet spinning method; soaking the graphene oxide fibers in a metal salt solution (the solvent is ethanol and water) (the soaking time is 30min-7 h); preparing different functionalized graphene fibers such as Cu/rGO and Fe through muffle furnace high-temperature reduction under inert gas2O3Functionalized graphene fibers such as/rGO, CoO/rGO, NiO/rGO and the like.
Description
Technical Field
The invention belongs to the field of ion exchange, and particularly relates to the field of preparation of functionalized graphene fibers.
Technical Field
In recent years, fibrous electronic textiles with multiple functions of sensing, driving, energy conversion, storage, data storage/transmission and the like have become a rapidly-developing research field, and have excellent application prospects in medical treatment, clinical diagnosis, on-site medical monitoring, intelligent wearable clothing, military and the like. Carbon fibers (typically graphene fibers) have been successfully used in fibrous devices such as electrocatalysis, supercapacitors and solar cells due to their light weight, good flexibility, environmental stability, high mechanical strength and electrical conductivity.
Conventionally, due to arrangement and overlapping accumulation of graphene nano sheets subjected to thermal reduction, graphene fibers are similar to naturally-existing solid carbon fibers and are difficult to further optimize, so that high-performance and multifunctional applications of the graphene nano sheets are limited. It is worth noting that the composite graphene and other nano materials (such as polymers, metals, metal oxides, etc.) can achieve synergistic effectThereby obtaining abundant unprecedented applications. In recent years, researchers have made many attempts to prepare multifunctional graphene composites by methods such as electrochemical precipitation, co-spinning, and the like. However, the graphene composites obtained by the two preparation methods cannot have a mixed fiber layered framework on a nanometer microscopic scale, so that the synergistic interaction between the graphene nanosheets and the electrochemically active material is limited. For example, when the active material is mixed with graphene first by a co-spinning method and then wet-spun, the active material is difficult to be mixed with graphene uniformly and is easy to agglomerate, and we effectively avoid this problem based on an ion exchange method, as shown in fig. 1, which is an SEM image of Ag/rGO fibers prepared by the co-spinning method. Similarly, the electrochemical precipitation method is high in cost and large in energy consumption, and the active material of the functionalized graphene prepared by the method is only adsorbed on the surface of the graphene and is easy to have the phenomenon of uneven adsorption, but the preparation method based on ion exchange is low in cost and low in energy consumption, and the active material is not only adsorbed on the surface of the graphene but also exists between graphene sheet plates, so that the overlapping problem of the graphene sheet plates is effectively solved, and more comprehensive functionalization is realized, for example, as shown in fig. 2, ZrO prepared by the electrochemical precipitation method is2SEM image of/rGO complex.
Disclosure of Invention
The invention aims to provide a novel preparation method of multifunctional graphene fiber based on ion exchange, which effectively solves the problem of overlapping of graphene sheets through the synergistic interaction between an active material and the graphene sheets, and realizes more comprehensive functionalization of graphene.
The invention provides a method for manufacturing multifunctional graphene fibers, which comprises the following steps:
preparing graphene oxide, and preparing graphene oxide fibers by a wet spinning method;
1 to 5 wt% of Cu (NO)3)2Or Fe (NO)3)3Or Co (NO)3)2Or Ni (NO)3)2Soaking the prepared graphene oxide fibers in a metal salt solution (solvent: ethanol and water) by using an ethanol aqueous solution;
and naturally drying the prepared metal ion composite graphene oxide fiber, and then carrying out thermal reduction through a muffle furnace. Carrying out heat treatment on Cu/GO fibers for 1-2h at 800 ℃ under the condition of argon-hydrogen mixed gas, and carrying out heat treatment on Fe/GO, Co/GO and Ni/GO fibers for 1-2h at 400 ℃ under the condition of argon respectively to obtain multifunctional graphene fibers;
the soaking time is 30min-7h (in Cu (NO)3)2Soaking in ethanol water solution for 30min to obtain Fe (NO)3)3Soaking in ethanol water solution for 7 h);
the metal salt solution solvent is ethanol and water in a volume ratio of 2: 1.
Has the advantages that:
the synthesis method adopts common raw materials with rich resources, thereby having lower cost and low energy consumption; the method for spontaneously carrying out ion exchange in the solution has mild reaction conditions, simple process and good reproducibility, not only effectively avoids the agglomeration problem in the co-spinning, but also effectively improves the phenomenon of uneven adsorption of an active material in an electrochemical deposition method, and more comprehensively realizes the functionalization of graphene.
Drawings
FIG. 1 is an SEM image of a co-spun Ag/rGO fiber;
FIG. 2 shows preparation of ZrO by electrochemical precipitation2SEM image of/rGO complex;
fig. 3 is an SEM image of the graphene fiber prepared by wet spinning of example 2;
FIG. 4 is an SEM image of Cu/rGO fibers prepared after ion exchange in example 3;
FIG. 5 is an SEM image of Cu/rGO fibers prepared after ion exchange in example 3
FIG. 6 is an XPS plot of Cu/rGO fibers prepared after ion exchange in example 3;
FIG. 7 shows Fe prepared after ion exchange in example 42O3SEM image of/rGO fiber;
FIG. 8 shows Fe prepared after ion exchange in example 42O3XPS plots of/rGO fibers;
FIG. 9 is an XPS plot of CoO/rGO fibers prepared after ion exchange in example 5;
FIG. 10 is an XPS plot of NiO/rGO fibers prepared after ion exchange in example 6;
the specific implementation mode is as follows:
the present invention will be further described with reference to the following examples, which are intended to illustrate the technical common general knowledge that the present invention can be described by other means without departing from the technical features of the present invention, and therefore all changes within the scope of the present invention or the equivalent scope of the present invention are intended to be embraced by the present invention.
Example 1:
preparing graphene oxide: dispersing 2g of graphite powder into 100mL of 98 mass percent concentrated sulfuric acid in an ice bath, slowly adding 10-12g of potassium permanganate while stirring, stirring for 1-1 hour at 30 ℃, then slowly dropwise adding 160mL of deionized water, heating and stirring for 30 minutes to 1 hour at 90 ℃ in an oil bath, adding 400mL of deionized water, and finally adding 12-15mL of 30 mass percent H2O2And stirring for 30 minutes, and repeatedly washing with HCl solution with the mass concentration of 5% and deionized water to obtain the colloidal graphene oxide.
| Serial number | Graphite powder (g) | 98% concentrated sulfuric acid ml | Potassium permanganate (g) | Adding deionized water ml for the first time | Adding deionized water ml for the second time | H2O2ml |
| 1 | 2 | 100 | 10 | 160 | 400 | 12 |
| 2 | 2 | 100 | 12 | 160 | 400 | 15 |
| 3 | 2 | 100 | 12 | 160 | 400 | 12 |
Example 2:
preparing graphene fibers: firstly, injecting 16-30mg/mL GO aqueous solution into a coagulation bath by an injection pump through a wet spinning method (the injection rate of the injection pump is 10-30 mu L/min), wherein the coagulation bath adopts saturated ethanol solution of potassium hydroxide to prepare the graphene oxide fiber. Heating at the speed of 2-10 ℃/min in a muffle furnace in an argon and hydrogen mixed gas environment, and reducing and oxidizing the graphene fibers at the temperature of 400-800 ℃ for 2-4 hours to obtain graphene fibers with good conductivity;
the microscopic morphology of the product of this example was observed by using a scanning electron microscope, and the result is shown in fig. 3, which is a partial enlarged view of graphene fibers reduced at 800 ℃ for 2 hours;
example 3:
preparation of Cu/rGO fibers: as shown in example 2, graphene oxide fibers were prepared and then immersed in 1-5 wt% Cu (NO)3)2And (2) naturally drying the soaked fiber in an ethanol aqueous solution for 30 minutes to 3 hours with the volume ratio of the ethanol to the water being 2:1, and finally heating at the speed of 2-10 ℃/min under the condition of a mixed gas of argon and hydrogen, and reducing at the temperature of 800-1000 ℃ for 2-4 hours to obtain the Cu/rGO fiber.
| Serial number | Cu(NO3)2Mass fraction (%) | Soaking time (h) |
| 1 | 1 | 3 |
| 2 | 3 | 3 |
| 3 | 5 | 0.5 |
The microscopic morphology of the product of the embodiment is observed by using a scanning electron microscope, the result is shown in fig. 4 and 5, the Cu nanoparticles are successfully distributed on the graphene fiber, the XPS test is performed on the graphene fiber, and the result is further shown in fig. 6 to prove that the product is a Cu/rGO fiber;
example 4:
Fe2O3preparation of/rGO fibres: as shown in example 2, graphene oxide fibers were prepared and then immersed in 1-5 wt% Fe (NO)3)3Adding ethanol water solution for 3-7 hr at a volume ratio of 2:1, naturally drying the soaked fiber, heating at 2-10 deg.C/min under argon gas condition, and reducing at 400-500 deg.C for 2-4 hr to obtain Fe2O3a/rGO fiber.
| Serial number | Fe(NO3)3Mass fraction (%) | Soaking time (h) |
| 1 | 1 | 3 |
| 2 | 3 | 3 |
| 3 | 5 | 7 |
The microscopic morphology of the product of this example was observed by scanning electron microscopy, and the result is shown in FIG. 7, where Fe2O3The nanoparticles are successfully distributed on the surface of the graphene and exist between graphene sheet plates, and XPS (X-ray diffraction) test is carried out on the nanoparticles, and the result is shown in FIG. 8 to further prove that the product is Fe2O3(ii)/rGO fiber;
example 5:
preparation of CoO/rGO fibers: as shown in example 2, graphene oxide fibers were prepared and then immersed in 1-5 wt% Co (NO)3)2And (2) soaking the fiber in an ethanol aqueous solution for 30 minutes to 3 hours at the volume ratio of the ethanol to the water of 2:1, naturally drying the soaked fiber, finally heating at the speed of 2-10 ℃/min under the condition of argon, and reducing at the temperature of 400-500 ℃ for 2-4 hours to obtain the CoO/rGO fiber.
| Serial number | Co(NO3)2Mass fraction (%) | Soaking time (h) |
| 1 | 1 | 3 |
| 2 | 3 | 3 |
| 3 | 5 | 0.5 |
XPS tests were conducted on the product of this example and the results are shown in FIG. 9, demonstrating that the product is a CoO/rGO fiber;
example 6:
preparation of NiO/rGO fibers: as shown in example 2, graphene oxide fibers were prepared and then immersed in 1-5 wt% Ni (NO)3)2In ethanol water solution for 30 minutes to 3 hours, the volume ratio of ethanol to water is 2:1, mixingAnd naturally drying the soaked fibers, finally heating at the speed of 2-10 ℃/min under the condition of argon, and reducing at the temperature of 400-500 ℃ for 2-4 hours to prepare the NiO/rGO fibers.
| Serial number | Ni(NO3)2Mass fraction (%) | Soaking time (h) |
| 1 | 1 | 3 |
| 2 | 3 | 3 |
| 3 | 5 | 0.5 |
XPS tests were conducted on the product of this example and the results are shown in FIG. 10, demonstrating that the product is a NiO/rGO fiber.
Claims (7)
1. The preparation method of the functionalized graphene based on ion exchange is characterized in that the functionalized graphene fiber is prepared by using graphene oxide as a precursor, performing wet spinning, then performing ion exchange with a metal salt solution, and finally performing high-temperature reduction, and specifically comprises the following steps:
(1) the method comprises the following steps of (1) adopting a wet spinning method, taking a graphene oxide aqueous solution as a spinning solution, and injecting the spinning solution into a coagulating bath through an injection pump to prepare graphene oxide fibers; the coagulating bath is saturated ethanol solution of potassium hydroxide;
(2) soaking the collected graphene oxide fibers in a metal salt solution; the metal salt solution is Cu (NO)3)2Ethanol aqueous solution or Fe2(NO3)3Aqueous ethanol solution or Co (NO)3)2Ethanol aqueous solution or Ni (NO)3)2Soaking the ethanol aqueous solution for 30 minutes to 7 hours, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is 2: 1;
(3) and reducing the mixture in a muffle furnace at high temperature under inert gas.
2. The preparation method of ion exchange-based functionalized graphene according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the graphene oxide fiber is prepared by a wet spinning method, and the spinning solution is a graphene oxide aqueous solution with the solubility of 16-30 mg/mL.
3. The preparation method of ion exchange-based functionalized graphene according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the graphene oxide fiber is prepared by a wet spinning method, and the injection rate of an injection pump is 10-30 mu L/min.
4. The method for preparing functionalized graphene based on ion exchange according to claim 1, wherein the soaking time in the step (2) is 30 minutes to 7 hours.
5. The method for preparing functionalized graphene based on ion exchange according to claim 1, wherein the method comprises the following steps: the mass fraction of the metal salt in the metal salt solution in the step (2) is 1-5 wt%.
6. The preparation method of ion exchange-based functionalized graphene according to claim 1, wherein the preparation method comprises the following steps: the metal salt solution in the step (2) is Cu (NO)3)2The Cu/rGO fiber in the step (3) is maintained at the temperature rise rate of 2-10 ℃/min and the temperature of 800-2-Ar mixed gasPrepared under bulk conditions.
7. The preparation method of ion exchange-based functionalized graphene according to claim 1, wherein the preparation method comprises the following steps: the metal salt solution in the step (2) is Fe2(NO3)3Or Co (NO)3)2Or Ni (NO)3)2Then Fe in step (3)2O3the/rGO or CoO/rGO or NiO/rGO fiber is prepared at the temperature rise rate of 2-10 ℃/min and the temperature of 400-500 ℃ for 2-4 hours under the Ar gas condition.
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| CN111705419B (en) * | 2020-06-28 | 2021-08-31 | 南京工业大学 | Metal-loaded carbon nitride-doped graphene-based flexible non-woven fabric and preparation method and application thereof |
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