CN107761081B - A kind of graphene/silver composite material of high-compactness and preparation method thereof - Google Patents
A kind of graphene/silver composite material of high-compactness and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to graphene composite material fields, disclose a kind of graphene/silver composite material and preparation method thereof of high-compactness.Graphene/silver composite material of the high-compactness and preparation method thereof obtains single-layer graphene oxide solution, prevents lamella discontinuous by twice ultrasonic dispersing technology, and " the carbon cake " of composition is mutually mixed for multilayer graphene oxide sheet；And using substrate as graphene oxide solution substrate, by growing silver or nano silver in graphene oxide substrate surface；The silver or nano silver of more high density and lower partial size, the present invention repeatedly react dipping substrate in order to obtain simultaneously, finally obtain graphene/composite material of high-compactness.
Description
Technical field
The present invention relates to graphene composite material fields, compound more particularly, to a kind of graphene/silver of high-compactness
Material and preparation method thereof.
Background technique
Graphene is a kind of bonding in the form of hexagon grid of the carbon atom by sp2 hydridization, is formed by the two dimension of carbon
Planar monolayer structure is the allotrope of carbon.Graphene is the basic unit for constructing other dimension carbon materials, when it is with packet
When the mode wrapped up in, wind and piled up changes, the fullerene of zero dimension, the stone of one-dimensional carbon nanotube and three-dimensional can be respectively formed
Ink.Graphene has good electricity-optics performance, mechanical property, heat-conductive characteristic and high electric charge carrier migration
Rate, while there are also outstanding mechanical strengths and flexibility.These properties of graphene allow it to be rapidly become by numerous concerns
The hot spot of research.The graphene and its derivative handled by chemical modification is even more the material with specific function, can be used for crystalline substance
Body pipe, liquid-crystal apparatus, electrochemica biological sensor, supercapacitor, fuel cell, solar battery etc..
Silver-based composite material is current most popular contact material.It is full since the mechanical property of fine silver is insufficient
Its requirement of foot, generallys use the reinforced phases such as metal oxide at present and silver compound prepares silver-based composite material.And add this
Its electric conductivity of the silver-based composite material of class reinforced phase decreases again.Graphene is presently found unique existing one kind by carbon
The environment-friendly type carbonaceous new material of bi-dimensional cellular shape lattice structure made of atom dense packing, thickness usually 10 nanometers with
It is interior, there is extra specific surface area (2630m 2 / g), it is to be currently known the highest material of intensity (up to 130GPa), current-carrying migration
Rate is up to 150,000cm 2 / Vs, thermal conductivity are up to 5150W (m K).Therefore, as can the excellent properties of graphene are introduced
Into silver-based composite material, tremendous influence will be carried out for the design and performance elevator belt of silver-based composite material.
Redox solution method is generallyd use in the prior art, uses graphene oxide for raw material, by anti-with silver nitrate
It after answering, then restores to obtain graphene/aluminium powder material by reducing agent, as Chinese patent CN201310648627.3 is disclosed
A kind of graphene/argentum nano composite material of high conductivity, discloses (1) and prepares graphene oxide, (2) prepare graphene oxide
Aqueous solution, (3) prepare graphene/silver nanoparticle conducing composite material.Graphene/aluminium powder that the above method and patent are prepared
Material, the silver metal or nano silver density of graphene surface growth are lower, partial size is not high, silver-colored or nano Silver quality percentage accounting
It is not high, and defect and hole are easily caused, seriously affect electric conductivity.
Summary of the invention
Technical problems to be solved of the invention are that be prepared into graphene/silver compound for prior art oxidation-reduction method
The problem that density of material is lower, partial size is not high, silver-colored or nano Silver quality percentage accounting is not high, provides a kind of stone of high-compactness
Black alkene/silver composite material preparation method.
The present invention also provides a kind of graphene/silver composite materials of high-compactness being prepared using the above method.
The purpose of the present invention is achieved by the following technical programs:
A kind of graphene/silver composite material preparation method of high-compactness is provided, comprising the following steps:
S1. prepare graphene oxide substrate: preparing graphene oxide using Hummers method is improved, be then dissolved in water into
The dispersion of row twice ultrasonic, obtains graphene oxide water solution；
It will be surface-treated, then be immersed in graphene oxide water solution by APTS after substrate cleaning, drying, obtained
Graphene oxide substrate；
S2. it configures silver nitrate reduction liquid: silver nitrate, sodium citrate and reducing agent being mixed, silver nitrate reduction liquid is obtained；
S3. graphene oxide substrate step S1 being prepared immerses in the silver nitrate reduction liquid of step S2, using nitrogen
Gas is purged, and after having reacted, is taken out dipping substrate, is then freeze-dried；
S4. using the substrate after being freeze-dried as object, step S2~S3 is repeated at least twice, then in hydrazine steam also
Original is cleaned after having reacted with deionized water, and graphene/silver composite material is obtained；
S5. it is heat-treated: the obtained graphene/silver composite material of step S4 being heat-treated, the stone of high-compactness is obtained
Black alkene/composite material；
It wherein, is all under atmosphere of inert gases during step S3~S5.
The present invention obtains single-layer graphene oxide solution, prevents lamella discontinuous, be more by twice ultrasonic dispersing technology
Layer graphene oxide sheet mutually mixes " the carbon cake " of composition；And using substrate as graphene oxide solution substrate, by oxygen
Graphite alkene substrate surface growth silver or nano silver；The silver or nano silver of more high density and lower partial size in order to obtain simultaneously,
Dipping substrate is repeatedly reacted in invention, finally obtains graphene/composite material of high-compactness.
Preferably, the dispersion of twice ultrasonic described in step S1 refers to that the temperature of first time ultrasonic disperse is 30 ~ 50 DEG C, frequency
It is 1.0 ~ 4.0m for 10000 ~ 25000 Hz, flow velocity3/ h, circulation stirring speed are 1000 ~ 2000 r/min, ultrasonic disperse time
For 0.5 ~ 2.0 h；The temperature of second of ultrasonic disperse is 30 ~ 50 DEG C, frequency is 18000 ~ 25000 Hz, flow velocity is 2.0 ~ 5.0
m3/ h, circulation stirring speed are 1000 ~ 2000 r/min, the ultrasonic disperse time is 2 ~ 5h.
Preferably, graphene oxide water solution described in step S1 be single-layer graphene oxide, concentration be 0.02~
0.04g/L。
Preferably, substrate described in step S1 is silicon carbide or oxidation silicon base.
Preferably, the concentration of silver nitrate described in step S2 is 0.1~0.3mol/L, the concentration of sodium citrate is 0.05~
0.1mol/L, the concentration of reducing agent are 0.1~0.3mol/L.
Preferably, the reducing agent is glucose.
Preferably, reaction temperature is 70~100 DEG C in step S3, and the reaction time is 10~30min.
Preferably, nitrogen purge time described in step S3 is 15~20min.
Preferably, the temperature of heat treatment described in step S5 is 200~220 DEG C, and the time is 1~2h.
The present invention also provides a kind of graphene/silver composite material of high-compactness being prepared using the above method, institutes
It states mass percent silver-colored in graphene/silver composite material and is up to 99.61%, density 10.44g/cm3, conductivity be 12~
34S/cm, silver granuel diameter are 20~43nm.
Compared with prior art, the beneficial effects of the present invention are:
Preparation process of the present invention is simple, by twice ultrasonic decentralized processing, obtains finely dispersed single-layer graphene oxide
Aqueous solution solves the problems, such as that prior art oxidation-reduction method is prepared into that graphene film lamella is discontinuous, overlapping, is conducive to subsequent anti-
It answers.
The present invention uses finely dispersed single-layer graphene oxide solution, reacts, passes through in substrate of glass after modification
APTS improves adhesive force without using other physical methods, ensure that silver or nano silver are additional in surface of graphene oxide
Stability, be conducive to silver particles surface of graphene oxide grow.
Core of the invention is to impregnate substrate as object, by repeatedly being restored in silver nitrate reduction liquid, greatly
Ground improves reaction efficiency, promotes surface of graphene oxide and grows fine and close silver nano-grain, reacts compared to single, conductive
Performance has quality raising.
The present invention uses small molecule sodium citrate, rather than stabilization of the polymer electrolyte compound as silver nano-grain surface
Agent enhances nano silver and contacts with the surface of graphene, to ensure that the electric conductivity of composite material, aoxidized with hydrazine hydrate reduction
Graphene, and the protective effect of sodium citrate effectively prevents the reunion of the Nano silver grain itself of reduction, while passing through model moral
The effect of Hua Li so that on graphene sheet layer can uniform growth in situ Nano silver grain, graphene after inhibiting reduction from
Body effectively enhances its electric conductivity while reunion.
The present invention, using the method for freeze-drying, effectively prevents in graphene oxide/silver composite material drying process
(reason is in graphene oxide that there are big calorimetrics to graphene oxide thermal weight loss under the reunion and destruction of graphene and high temperature
The oxygen-containing functional group of stability difference)；The present invention carries out annealing heat-treatment to the graphene after reduction/argentum nano composite material, into
Facilitate structural improvement to one step, to enhance electric conductivity.
Detailed description of the invention
Fig. 1 the first ultrasonic device structural schematic diagram.
Fig. 2 the second ultrasonic device structural schematic diagram.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.Following embodiment is only illustrative examples, not structure
At inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and be covered by summary of the invention is implemented.Unless special
Do not mentionlet alone bright, reagent, compound and the equipment that the present invention uses is the art conventional reagent, compound and equipment.
Embodiment 1
The present embodiment provides a kind of graphene/silver composite material preparation methods of high-compactness, comprising the following steps:
S1. prepare graphene oxide substrate: preparing graphene oxide using Hummers method is improved, be then dissolved in water into
The dispersion of row twice ultrasonic, obtains aqueous solution of single-layer grapheme oxide, concentration 0.02g/L；
After silicon carbide or silica substrate cleaning, drying, immerses in APTS ethanol solution, complete surface treatment, then soak
Enter into graphene oxide water solution, obtains graphene oxide substrate；
S2. silver nitrate reduction liquid is configured: by 0.1mol/L silver nitrate, 0.05mol/L sodium citrate and 0.1mol/L grape
Sugar mixing, obtains silver nitrate reduction liquid；
S3. graphene oxide substrate step S1 being prepared immerses in the silver nitrate reduction liquid of step S2, reaction temperature
Degree is 70 DEG C, and reaction time 10min is purged using nitrogen, purge time 15min, after having reacted, takes out dipping base
Then bottom is freeze-dried；
S4. using the substrate after being freeze-dried as object A, the nitre that is again dipped into the silver nitrate reduction liquid of step S2 or newly configures
It in sour silver reducing solution, is purged using nitrogen, after having reacted, takes out dipping substrate, then freeze-drying obtains object B, will
Object B reductase 12 4h in 100 DEG C of hydrazine steam, is cleaned with deionized water after having reacted, obtains graphene/silver composite material；
S5. it is heat-treated: the obtained graphene/silver composite material of step S4 is heat-treated, temperature is 200 DEG C, the time
For 1h, graphene/composite material of high-compactness is obtained；
It wherein, is all specially one kind of nitrogen, argon gas, helium under atmosphere of inert gases during step S3~S5
Or it is a variety of；
Silver ion reduction, as reducing agent, is become silver nano-grain, to be grown in oxygen using glucose by the present embodiment
Fossil mertenyl bottom, using small molecule sodium citrate, rather than stabilizer of the polymer electrolyte compound as silver nano-grain surface,
It enhances nano silver to contact with the surface of graphene, to ensure that the electric conductivity of composite material, by repeatedly reacting greatly
Reaction efficiency is improved, surface of graphene oxide is promoted and grows fine and close silver nano-grain, cooperation freeze-drying can be effective
It avoids functional group in graphene oxide from being destroyed, causes thermal weight loss, graphene oxide is then reduced by reduction by hydrazine steam
Graphene oxide finally obtains the graphene/silver composite material of high-compactness.
Wherein, twice ultrasonic dispersion refers to that the temperature of first time ultrasonic disperse is 30 ~ 50 DEG C, frequency is in step S1
10000 ~ 25000 Hz, flow velocity are 1.0 ~ 4.0m3/ h, circulation stirring speed are 1000 ~ 2000 r/min, the ultrasonic disperse time is
0.5~2.0 h；The temperature of second of ultrasonic disperse is 30 ~ 50 DEG C, frequency is 18000 ~ 25000 Hz, flow velocity is 2.0 ~ 5.0
m3/ h, circulation stirring speed are 1000 ~ 2000 r/min, the ultrasonic disperse time is 2 ~ 5h.
As shown in Fig. 1~2, the present embodiment also provides a kind of twice ultrasonic dispersing apparatus, including the first ultrasonic device and
Two ultrasonic devices, the first ultrasonic device include the first circulation system in the first mixing pond 1 and multiple first ultrasonic reaction kettles composition,
First ultrasonic reaction kettle includes Vltrasonic device 3 and reaction kettle 4, and the first mixing pond 1 is equipped with feeding port 101, and upper end passes through pipeline 2
It is connect with the first ultrasonic reaction kettle, lower end passes through pipeline 6 respectively and connects the first ultrasonic reaction kettle, pipeline 7 and the first discharge port 8 company
It connects, pipeline 6 is equipped with centrifugal pump 61 and flowmeter 62, and multiple first ultrasonic reaction kettles are in difference in height arrangement connection, wherein horizontal
It is connected between position minimum the first ultrasonic reaction kettle and pipeline 7 by pipeline 9；
Second ultrasonic device includes the second circulation system in the second mixing pond 10 and multiple second ultrasonic reaction kettles composition, the
Two ultrasonic reaction kettles are identical as the first ultrasonic reaction kettle structure, and the upper end in the second mixing pond passes through pipeline 11 and the second ultrasonic reaction
Kettle connection, lower end is connect with pipeline 12；Pipeline 12 is equipped with feed inlet 13, the centrifugal pump 14, flow connecting with the first discharge port 8
Meter 15 and the second discharge port 16, the second ultrasonic reaction kettle horizontal position are sequentially connected, and are equipped with exhaust valve, and pass through pipeline 17
It is connect with pipeline 12, wherein the first ultrasonic device and the second ultrasonic device further include multiple ball valves 18 being arranged on pipeline.
The present embodiment ultrasonic disperse equipment controls frequency and temperature by Vltrasonic device 3, and centrifugal pump carrys out coutroi velocity, the
One, blender in the second mixing pond controls mixing speed, is then carried out step by step by control ball valve to realize.
Embodiment 2
The present embodiment provides a kind of graphene/silver composite material preparation methods of high-compactness, comprising the following steps:
S1. prepare graphene oxide substrate: preparing graphene oxide using Hummers method is improved, be then dissolved in water into
The dispersion of row twice ultrasonic, obtains aqueous solution of single-layer grapheme oxide, concentration 0.04g/L；
After silicon carbide or silica substrate cleaning, drying, immerses in APTS ethanol solution, complete surface treatment, then soak
Enter into graphene oxide water solution, obtains graphene oxide substrate；
S2. silver nitrate reduction liquid is configured: by 0.3mol/L silver nitrate, 0.1mol/L sodium citrate and 0.3mol/L glucose
Mixing, obtains silver nitrate reduction liquid；
S3. graphene oxide substrate step S1 being prepared immerses in the silver nitrate reduction liquid of step S2, reaction temperature
Degree is 100 DEG C, and reaction time 30min is purged using nitrogen, purge time 20min, after having reacted, takes out dipping
Then substrate is freeze-dried；
S4. using the substrate after being freeze-dried as object A, the nitre that is again dipped into the silver nitrate reduction liquid of step S2 or newly configures
It in sour silver reducing solution, is purged using nitrogen, after having reacted, takes out dipping substrate, then freeze-drying obtains object B, will
Object B reductase 12 4h in 100 DEG C of hydrazine steam, is cleaned with deionized water after having reacted, obtains graphene/silver composite material；
S5. it is heat-treated: the obtained graphene/silver composite material of step S4 is heat-treated, temperature is 220 DEG C, the time
For 2h, graphene/composite material of high-compactness is obtained；
It wherein, is all specially one kind of nitrogen, argon gas, helium under atmosphere of inert gases during step S3~S5
Or it is a variety of；
Wherein, twice ultrasonic dispersion refers to that the temperature of first time ultrasonic disperse is 30 ~ 50 DEG C, frequency is in step S1
10000 ~ 25000 Hz, flow velocity are 1.0 ~ 4.0m3/ h, circulation stirring speed are 1000 ~ 2000 r/min, the ultrasonic disperse time is
0.5~2.0 h；The temperature of second of ultrasonic disperse is 30 ~ 50 DEG C, frequency is 18000 ~ 25000 Hz, flow velocity is 2.0 ~ 5.0
m3/ h, circulation stirring speed are 1000 ~ 2000 r/min, the ultrasonic disperse time is 2 ~ 5h.
Embodiment 3
The present embodiment is substantially the same manner as Example 1, the difference is that, it is 3 that step S2~S4 number is repeated in step S4
It is secondary.
Embodiment 4
The present embodiment is substantially the same manner as Example 1, the difference is that, it is 4 that step S2~S4 number is repeated in step S4
It is secondary.
Embodiment 5
The present embodiment is substantially the same manner as Example 1, the difference is that, it is 5 that step S2~S4 number is repeated in step S4
It is secondary.
Comparative example 1
This comparative example is substantially the same manner as Example 1, the difference is that, a ultrasonic disperse, temperature are used in step S2
For 30 ~ 50 DEG C, frequency be 10000 ~ 25000 Hz, flow velocity is 1.0 ~ 4.0m3/ h, circulation stirring speed are 1000 ~ 2000 r/
Min, ultrasonic disperse time are 0.5 ~ 2.0 h.
Comparative example 2
This comparative example is substantially the same manner as Example 1, the difference is that, step S4 is using the substrate after being freeze-dried as object
A, the reductase 12 4h in 100 DEG C of hydrazine steam, is cleaned with deionized water after having reacted, obtains graphene/silver composite material.
Comparative example 3
This comparative example is substantially the same manner as Example 1, the difference is that, the heat treatment without step S5.
Performance characterization: material is carried out to the graphene/silver composite material that Examples 1 to 5 and comparative example 1~3 are prepared
Expect performance test, the results are shown in Table 1:
Table 1
| Embodiment | Silver-colored (wt%) | Density (g/cm3) | Conductivity (S/cm) | Silver granuel diameter (nm) |
| Embodiment 1 | 99.31 | 10.41 | 34 | 20 |
| Embodiment 2 | 99.40 | 10.42 | 21 | 31 |
| Embodiment 3 | 99.52 | 10.43 | 12 | 38 |
| Embodiment 4 | 99.59 | 10.44 | 12 | 43 |
| Embodiment 5 | 99.61 | 10.44 | 12 | 43 |
| Comparative example 1 | 82.65 | 8.67 | 72 | 200 |
| Comparative example 2 | 85.35 | 9.11 | 81 | 78 |
| Comparative example 3 | 91.25 | 9.57 | 82 | 100 |
Claims (7)
1. a kind of graphene/silver composite material preparation method of high-compactness, which comprises the following steps:
S1. it prepares graphene oxide substrate: preparing graphene oxide using Hummers method is improved, be then dissolved in water and carry out two
Secondary ultrasonic disperse, twice ultrasonic dispersion refer to the temperature of first time ultrasonic disperse be 30~50 DEG C, frequency be 10000~
25000Hz, flow velocity are 1.0~4.0m3/ h, circulation stirring speed are 1000~2000r/min, the ultrasonic disperse time be 0.5~
2.0h；The temperature of second of ultrasonic disperse is 30~50 DEG C, frequency is 18000~25000Hz, flow velocity is 2.0~5.0m3/h、
Circulation stirring speed is 1000~2000r/min, the ultrasonic disperse time is 2~5h, obtains graphene oxide water solution, the oxygen
Graphite aqueous solution concentration is 0.02~0.04g/L；
It will be surface-treated, then be immersed in graphene oxide water solution by APTS after substrate cleaning, drying, aoxidized
Graphene-based bottom；
S2. it configures silver nitrate reduction liquid: silver nitrate, sodium citrate and reducing agent being mixed, silver nitrate reduction liquid, the nitre are obtained
The concentration of sour silver is 0.1~0.3mol/L, and the concentration of sodium citrate is 0.05~0.1mol/L, the concentration of reducing agent is 0.1~
0.3mol/L；
S3. graphene oxide substrate step S1 being prepared immerses in the silver nitrate reduction liquid of step S2, using nitrogen into
Row purging after having reacted, takes out dipping substrate, is then freeze-dried；
S4. it using the substrate after being freeze-dried as object, repeats step S2~S3 at least twice, is then restored in hydrazine steam, instead
It is cleaned after having answered with deionized water, obtains graphene/silver composite material；
S5. it is heat-treated: the obtained graphene/silver composite material of step S4 is heat-treated, the temperature of the heat treatment is 200
~220 DEG C, the time is 1~2h, obtains the graphene/silver composite material of high-compactness；
It wherein, is all under atmosphere of inert gases during step S3~S5.
2. the graphene/silver composite material preparation method of high-compactness according to claim 1, which is characterized in that step S1
Described in graphene oxide water solution be single-layer graphene oxide.
3. the graphene/silver composite material preparation method of high-compactness according to claim 1, which is characterized in that step S1
Described in substrate be silicon carbide or oxidation silicon base.
4. the graphene/silver composite material preparation method of high-compactness according to claim 1, which is characterized in that described to go back
Former agent is glucose.
5. the graphene/silver composite material preparation method of high-compactness according to claim 1, which is characterized in that step S3
Middle reaction temperature is 70~100 DEG C, and the reaction time is 10~30min.
6. the graphene/silver composite material preparation method of high-compactness according to claim 1, which is characterized in that step S3
Described in nitrogen purge time be 15~20min.
7. a kind of graphene/silver composite material of high-compactness, which is characterized in that the height as described in claim 1~6 any one
The graphene/silver composite material preparation method of consistency is prepared.
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| CN110237726A (en) * | 2019-06-26 | 2019-09-17 | 兰州理工大学 | A kind of polysulfones/graphene oxide/carbon nanotube mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof |
| CN110477012B (en) * | 2019-08-22 | 2021-05-18 | 河南省人民医院 | GO-PEG/Ag-SD composite material and preparation method and application thereof |
| CN111678906A (en) * | 2020-06-15 | 2020-09-18 | 青岛峰峦新材料科技有限责任公司 | MoS2Surface-enhanced Raman substrate made of Ag-N-doped graphene nanocomposite and preparation method thereof |
| CN112151285B (en) * | 2020-09-04 | 2023-06-20 | 安徽壹石通材料科技股份有限公司 | Silver-based electric contact material with two-dimensional lamellar phase enhancement and preparation method thereof |
| CN117364063B (en) * | 2023-10-27 | 2024-05-10 | 无锡松煜科技有限公司 | Silver powder and preparation method and application thereof |
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