CN106894112B - A kind of graphene fiber and preparation method thereof of nanometer of modified by silver - Google Patents
A kind of graphene fiber and preparation method thereof of nanometer of modified by silver Download PDFInfo
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- CN106894112B CN106894112B CN201510955263.2A CN201510955263A CN106894112B CN 106894112 B CN106894112 B CN 106894112B CN 201510955263 A CN201510955263 A CN 201510955263A CN 106894112 B CN106894112 B CN 106894112B
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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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
Abstract
The invention discloses the graphene fiber of a kind of nanometer of modified by silver, it is a kind of coating surface graphene fiber that have average diameter be 1-100nm, the nano-silver layer with a thickness of 10-1000nm and fiber overall diameter are 3-200 μm.Its preparation process includes the preparation of graphene oxide spinning solution, spinning graphene oxide fiber, preparation nanometer modified by silver graphene oxide glue fiber and four preparation steps of graphene fiber for preparing nanometer modified by silver.The fiber has the excellent characteristics of nano silver and graphene simultaneously, and is fibre morphology, has extremely wide application prospect in fields such as structure enhancing, microelectronics, Heat Conduction Material, radiation protection and weavings.
Description
Technical field
The invention belongs to fibrous material fields.It is related to a kind of graphene fiber, the stone of especially a kind of nanometer modified by silver
Black alkene fiber and preparation method thereof.
Background technique
Graphene is the two-dimensional material of only one carbon atom thickness, it is the nanometer that known world is most thin, most hard
Material.It is almost fully transparent, the light of absorption 2.3%；Thermal coefficient is up to 5300W/mK, be higher than carbon nanotube and
Diamond；Its electron mobility is more than 15000cm2/Vs under room temperature, and higher than carbon nanotubes or silicon crystal；And resistivity is only
About 10-8 Ω m, it is lower than copper or silver, it is the smallest material of world resistivity.Since its excellent light, electricity, heat and mechanics are special
Property, graphene is in structure enhancing, integrated circuit, transistor, conductive electrode, Heat Conduction Material, supercapacitor, filtering, solar energy
The fields such as battery, biological devices, photosensitive part all have the purposes having a high potential extensively.
Nano-Ag particles are due to its own quantum size effect, skin effect and its excellent electricity, light, heat and catalytic
Can, have on metal electrode, catalysis, optics, microelectronics, bio-sensing, antibacterial and raising solar battery conversion ratio huge
Application value.
In order to close the characteristic of nano silver using graphene simultaneously, prior art compound can prepare graphene conjunction nano silver
Graphene-silver composite material, such as CN201410667164.X, CN201410565546.1, CN201410565427.6.But
All it is two-dimensional sheet material or three-dimensional net structure by graphene-silver composite material prepared by these technologies, applies and add
Work performance all can not show a candle to one-dimensional fibrous material.
Summary of the invention
The object of the present invention is to provide a kind of graphene fiber, the graphene fiber of especially a kind of nanometer modified by silver and its
Preparation method.This fiber is not only provided simultaneously with highly conductive, the thermally conductive and optical characteristics of graphene and nano silver, and has nanometer
The antibacterial of silver, catalysis isoreactivity, in structure enhancing, microelectronics, electrode, Heat Conduction Material, supercapacitor, filtering, solar-electricity
The fields such as pond, biological devices, bio-sensing, optical component, radiation protection, weaving have extremely wide application prospect.
The technical solution that the present invention solves technical problem is as follows:
The graphene fiber of a kind of nanometer of modified by silver, it is that have average diameter be 10-100nm, thickness for a kind of coating surface
The graphene fiber that nano-silver layer and fiber overall diameter for 100-1000nm are 30-200 μm.
The graphene fiber of a kind of nanometer of modified by silver, preparation step are as follows:
The preparation of step (1) graphene oxide spinning solution: graphene oxide is evenly dispersed in deionized water, it is made dense
Degree is the graphene oxide spinning solution of 5-30mg/mL.
Step (2) spins graphene oxide fiber: it is 5- that the graphene oxide spinning solution of step (1) preparation, which is passed through diameter,
5000 μm, the spin duct that length is 5-100cm, are squeezed into coagulating bath with the speed of 10-100mL/min, stop 500-3600s,
Then it is cleaned, graphene oxide glue fiber is made.
Step (3) prepares nanometer modified by silver graphene oxide glue fiber: the graphene oxide of step (2) preparation is gluey
Fiber immerse silver ammino solution in, reducing agent is then added, under the conditions of 30-90 DEG C by silver ion reduction be nano-Ag particles, also
The former time is 50-180min, then cleans fiber, and obtained surface has the graphene oxide colloid of nanometer modified by silver fine
Dimension.
The graphene fiber of step (4) preparation nanometer modified by silver: by the graphite of the nanometer modified by silver of the step (3) preparation
Alkene glue fiber is dried in vacuo under the conditions of 40-100 DEG C, becomes solid graphite alkene fiber, and in 500-900 DEG C of temperature
Further by graphene oxide fiber in the inert gases such as nitrogen, argon gas or in the mixed atmosphere of inert gas and hydrogen under degree
It is reduced to the graphene fiber of nanometer modified by silver, recovery time 3-12h.
The preparation method of graphene oxide described in step (1) can for Hummer method, improve hummer method or
One of Staudenmair method.
It is 40-120 DEG C that coagulating bath described in step (2), which is temperature, contains sodium hydroxide, potassium hydroxide, calcium chloride or sulphur
The alcoholic solution or aqueous solution of one of sour copper, wherein sodium hydroxide, potassium hydroxide, calcium chloride, copper sulphate are in coagulating bath
Mass content is respectively 2-10%.
Cleaning process described in step (2) and step (3), the cleaning agent used are deionized water or alcohol organic solvent.
Silver ammino solution described in step (3) is to contain 10-90g/L silver nitrate, 2-60g/L sodium hydroxide and 5-20ml/L ammonia
The aqueous solution of water.
Reducing agent described in step (3) is glucose, sodium citrate or formalin.
The beneficial effects of the present invention are:
The graphene fiber of a kind of nanometer of modified by silver provided by the present invention has the excellent of nano silver and graphene simultaneously
Characteristic, in structure enhancing, microelectronics, electrode, Heat Conduction Material, supercapacitor, filtering, solar battery, biological devices, biology
The fields such as sensing, optical component, radiation protection have extremely wide application prospect.And due to its fibre morphology, product is processable
Property be improved, the programmable two-dimentional textile of structure or three-dimensional structure product can be further processed into, further opened up
Its applicability and application range are opened up.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the silver-colored polyimide fiber of present invention metallization
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, it should be appreciated that these embodiments are only limitted to illustrate
The present invention rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, this field
Technical staff can make various changes or modification to the present invention, these equivalences equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of graphene fiber of nanometer of modified by silver, it be a kind of coating surface have average diameter be 10nm, with a thickness of
The graphene fiber that the nano-silver layer and fiber overall diameter of 100nm is 30 μm, preparation step are as follows:
The preparation of step (1) graphene oxide spinning solution: graphene oxide is evenly dispersed in deionized water, it is made dense
Degree is the graphene oxide spinning solution of 5mg/ml.
Step (2) spins graphene oxide fiber: being by diameter by graphene oxide spinning solution prepared by step (1)
500 μm, the spin duct that length is 5cm squeeze into aqueous solution of the temperature for 40 DEG C and containing 5% calcium chloride with the speed of 10ml/min
In coagulating bath, 500s is stopped, then it is cleaned with a large amount of deionized waters, graphene oxide glue fiber is made.
Step (3) prepares nanometer modified by silver graphene oxide glue fiber: the graphene oxide of step (2) preparation is gluey
Fiber immerses in the silver ammino solution containing 10g/l silver nitrate, 2g/l sodium hydroxide and 5ml/l ammonium hydroxide, and glucose water is then added
Silver ion reduction is at room temperature nano-Ag particles, recovery time 50min, then with a large amount of deionizations by solution reduction agent
Water cleans fiber, and there is the graphene oxide colloid fiber of nanometer modified by silver on obtained surface.
The graphene fiber of step (4) preparation nanometer modified by silver: by the graphite of the nanometer modified by silver of the step (3) preparation
Alkene glue fiber is dried in vacuo under the conditions of 40 DEG C, becomes solid graphite alkene fiber；And under the conditions of 500 DEG C of temperature
It is further the graphene fiber of nanometer modified by silver, recovery time 3h by graphene oxide fiber reduction in nitrogen.
Embodiment 2
A kind of graphene fiber of nanometer of modified by silver, it be a kind of coating surface have average diameter be 55nm, with a thickness of
The graphene fiber that the nano-silver layer and fiber overall diameter of 550nm is 115 μm, preparation step are as follows:
The preparation of step (1) graphene oxide spinning solution: graphene oxide is evenly dispersed in deionized water, it is made dense
Degree is the graphene oxide spinning solution of 17mg/mL.
Step (2) spins graphene oxide fiber: being by diameter by graphene oxide spinning solution prepared by step (1)
2700 μm, the spin duct that length is 52cm squeeze into first of the temperature for 80 DEG C and containing 6% sodium hydroxide with the speed of 55mL/min
In alcoholic solution coagulating bath, 2000s is stopped, then it is cleaned with a large amount of second alcohol and waters, it is gluey fine that graphene oxide is made
Dimension.
Step (3) prepares nanometer modified by silver graphene oxide glue fiber: the graphene oxide of step (2) preparation is gluey
Fiber immerses in the silver ammino solution containing 50g/L silver nitrate, 30g/L sodium hydroxide and 12mL/L ammonium hydroxide, and citric acid is then added
Silver ion reduction is nano-Ag particles, recovery time 120min, then with largely going at 60 DEG C by sodium water solution reducing agent
Ionized water cleans fiber, and there is the graphene oxide colloid fiber of nanometer modified by silver on obtained surface.
The graphene fiber of step (4) preparation nanometer modified by silver: by the graphite of the nanometer modified by silver of the step (3) preparation
Alkene glue fiber is dried in vacuo under the conditions of 70 DEG C, becomes solid graphite alkene fiber；And under the conditions of 700 DEG C of temperature
It is further the graphene fiber of nanometer modified by silver, reduction by graphene oxide fiber reduction in the mixed atmosphere of argon gas and hydrogen
Time is 7h.
Embodiment 3
A kind of graphene fiber of nanometer of modified by silver, it be a kind of coating surface have average diameter be 100nm, with a thickness of
The graphene fiber that the nano-silver layer and fiber overall diameter of 1000nm is 200 μm, preparation step are as follows:
The preparation of step (1) graphene oxide spinning solution: graphene oxide is evenly dispersed in deionized water, it is made dense
Degree is the graphene oxide spinning solution of 30mg/ml.
Step (2) spins graphene oxide fiber: being by diameter by graphene oxide spinning solution prepared by step (1)
5000 μm, the spin duct that length is 100cm, squeezing into temperature with the speed of 100ml/min is 120 DEG C and containing 10% calcium chloride
In aqueous coagulation bath, 3600s is stopped, then it is cleaned with a large amount of deionized waters, it is gluey fine that graphene oxide is made
Dimension.
Step (3) prepares nanometer modified by silver graphene oxide glue fiber: the graphene oxide of step (2) preparation is gluey
Fiber immerses in the silver ammino solution containing 90g/l silver nitrate, 60g/l sodium hydroxide and 20ml/l ammonium hydroxide, and glucose is then added
Silver ion reduction is at room temperature nano-Ag particles by aqueous solution reducing agent, recovery time 180min, then with it is a large amount of go from
Sub- water cleans fiber, and there is the graphene oxide colloid fiber of nanometer modified by silver on obtained surface.
The graphene fiber of step (4) preparation nanometer modified by silver: by the graphite of the nanometer modified by silver of the step (3) preparation
Alkene glue fiber is dried in vacuo under the conditions of 100 DEG C, becomes solid graphite alkene fiber；And in 590 DEG C of temperature conditions
It is further the graphene fiber of nanometer modified by silver, recovery time 12h by graphene oxide fiber reduction in lower nitrogen.
Claims (6)
1. the graphene fiber of a kind of nanometer of modified by silver, characterized in that it is that have average diameter be 1- for a kind of coating surface
The graphene fiber that 100nm, the nano-silver layer with a thickness of 10-1000nm and fiber overall diameter are 3-200 μm；The nano silver is repaired
The preparation step of the graphene fiber of decorations are as follows:
The preparation of step (1) graphene oxide spinning solution: graphene oxide is evenly dispersed in deionized water, and obtained concentration is
The graphene oxide spinning solution of 0.05-30mg/mL；
Step (2) spins graphene oxide fiber: it is 5-5000 that the graphene oxide spinning solution of step (1) preparation, which is passed through diameter,
μm, length be 0.5-100cm spin duct, squeezed into coagulating bath with the speed of 0.1-100mL/min, stop 5-3600s, then
It is cleaned, graphene oxide glue fiber is made；
Step (3) prepares nanometer modified by silver graphene oxide glue fiber: graphene oxide glue fiber prepared by step (2)
It immerses in silver ammino solution, reducing agent is then added, by silver ion reduction be nano-Ag particles under the conditions of 10-90 DEG C, when reduction
Between be 5-180min, then fiber is cleaned, there is the graphene oxide colloid fiber of nanometer modified by silver on obtained surface；
The graphene fiber of step (4) preparation nanometer modified by silver: by the graphene glue of the nanometer modified by silver of the step (3) preparation
Shape fiber is dried in vacuo under the conditions of 40-100 DEG C, becomes solid graphite alkene fiber, and at a temperature of 500-900 DEG C
Further it is by graphene oxide fiber reduction in nitrogen, argon inert gas or in the mixed atmosphere of inert gas and hydrogen
The graphene fiber of nanometer modified by silver, recovery time 1-12h.
2. the graphene fiber of a kind of nanometer of modified by silver according to claim 1, characterized in that in its preparation step (1)
The preparation method of the graphene oxide can be Hummer method, improvement one of hummer method or Staudenmair method.
3. the graphene fiber of a kind of nanometer of modified by silver according to claim 1, characterized in that in its preparation step (2)
The coagulating bath is that temperature is 0-120 DEG C, the alcohol containing one of sodium hydroxide, potassium hydroxide, calcium chloride or copper sulphate
Solution or aqueous solution, wherein the mass content of sodium hydroxide, potassium hydroxide, calcium chloride, copper sulphate in coagulating bath be respectively
0.5-10%.
4. the graphene fiber of a kind of nanometer of modified by silver according to claim 1, characterized in that its preparation step (2) and
Cleaning process described in step (3), the cleaning agent used are deionized water or alcohol organic solvent.
5. the graphene fiber of a kind of nanometer of modified by silver according to claim 1, characterized in that its preparation step (3) institute
The silver ammino solution stated is to contain 10-90g/L silver nitrate, the aqueous solution of 2-60g/L sodium hydroxide and 0.5-20mL/L ammonium hydroxide.
6. the graphene fiber of a kind of nanometer of modified by silver according to claim 1, characterized in that its preparation step (3) institute
The reducing agent stated is glucose, sodium citrate or formalin.
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| CN108286188B (en) * | 2017-12-13 | 2020-07-03 | 深圳市源兴医药股份有限公司 | Silver-loaded graphene material and preparation method thereof |
| CN107915221A (en) * | 2017-12-13 | 2018-04-17 | 天津宝兴威科技股份有限公司 | A kind of preparation method of the strong stannic oxide/graphene nano ag material of antibiotic property |
| CN110644230B (en) * | 2019-09-12 | 2022-03-18 | 北京服装学院 | Ag nanoparticle-loaded graphene fiber and preparation method thereof |
| CN113122961B (en) * | 2021-05-26 | 2022-02-08 | 南通大学 | Preparation method of silver/graphene composite fiber |
| CN113470986B (en) * | 2021-07-19 | 2022-04-12 | 重庆文理学院 | Flexible linear supercapacitor and preparation method thereof |
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| CN104148666A (en) * | 2014-07-26 | 2014-11-19 | 哈尔滨工业大学 | Method for modifying graphene through nano-sliver |
| CN104308177A (en) * | 2014-10-14 | 2015-01-28 | 钱景 | Preparation method of graphene-loaded nano-silver composite material |
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| CN101067216A (en) * | 2007-06-12 | 2007-11-07 | 江苏盛虹化纤有限公司 | Strong elastic polyester continuous filament |
| CN103726133A (en) * | 2014-01-02 | 2014-04-16 | 东华大学 | High-strength, compact and ordered porous graphene fiber and continuous preparation method thereof |
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| CN104308177A (en) * | 2014-10-14 | 2015-01-28 | 钱景 | Preparation method of graphene-loaded nano-silver composite material |
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