CN107833756B - A kind of preparation method and applications of carbon fiber/three-dimensional netted graphene composite material - Google Patents
A kind of preparation method and applications of carbon fiber/three-dimensional netted graphene composite material Download PDFInfo
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- CN107833756B CN107833756B CN201710894122.3A CN201710894122A CN107833756B CN 107833756 B CN107833756 B CN 107833756B CN 201710894122 A CN201710894122 A CN 201710894122A CN 107833756 B CN107833756 B CN 107833756B
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of carbon fiber/three-dimensional netted graphene composite material preparation method and applications, pass through coating and heat-treating methods, there is porous and laminate structure graphene in carbon fiber surface growth, three-dimensional grapheme lamellar structure and carbon fiber form reticular structure.Structure specific surface area with higher, while can be realized the quick transmission of electronics and electrolyte ion, improve capacitive property.Carbon fiber of the present invention/three-dimensional netted graphene composite material not only can be directly as electrode material, but also can be used as a kind of conductive substrates, by growing other electrode materials, further applies in supercapacitor.
Description
Technical field
The present invention relates to a kind of carbon fiber/three-dimensional netted graphene composite material preparation method and applications, belong to and receive
Rice field of material technology.
Background technique
As a kind of novel green energy-storing device, electric chemical super capacitor is because having high power density, high charge-discharge
The features such as efficiency, big charge-discharge magnification, long-life, obtain extensive concern.Electrode material is to determine super capacitor electrode
One of an important factor for chemical stability, power density and energy density is current research hotspot.Carbon material is as a kind of normal
The electrode material for super capacitor seen, specific surface area with higher, preferable stability and longer cycle life.Carbon material
Various structures, such as carbon nanotube, block absorbent charcoal, carbon ball and lamellar graphite alkene etc..Wherein carbon fiber is a kind of with fibre
Form is tieed up, phosphorus content is high, the carbon material haveing excellent performance, and has small density, light weight, chemical stability and mechanical property outstanding
The advantages such as energy, so as to cause extensive concern.However, carbon fiber specific surface area is smaller, capacitor quality is relatively low, directly as super
Capacitor electrode material, chemical property are poor.
Therefore, how to increase carbon fiber specific surface area, improve carbon fiber as electrode material in the practical fortune of supercapacitor
With middle effect, there is important research meaning.
Summary of the invention
The purpose of the present invention is to provide a kind of carbon fiber/three-dimensional netted graphene composite material preparation method and its answer
With.For the present invention by coating and heat-treating methods, growing in carbon fiber surface has porous and laminate structure graphene, and three
It ties up graphene sheet layer structure and carbon fiber forms reticular structure.Structure specific surface area with higher, while can be realized electricity
The quick transmission of son and electrolyte ion improves capacitive property.Carbon fiber of the present invention/three-dimensional netted graphene composite material is not only
Can be directly as electrode material, and can be used as a kind of conductive substrates, by growing other electrode materials, further use
In supercapacitor.
Carbon fiber of the present invention/three-dimensional netted graphene composite material preparation method, includes the following steps:
Step 1: weighing PVA 0~6g of solid, be warming up to 70-90 DEG C of stirring and dissolving after adding distilled water 30ml, it is molten to obtain PVA
Liquid；KOH solid is dissolved in 10-30ml distilled water, is then mixed with PVA solution, in 60-80 DEG C of stirring 10-300min, is obtained
Obtain PVA-KOH solution；
Step 2: weighing 0.1~5g of glucose powder, 0.01~1g of 0.01~1.5g of red phosphorus and nickel acetate, 20- is added
The mixing of 30ml distilled water, stirs 10-300min at 50-80 DEG C, until solution in thick, obtains glucose-red phosphorus-nickel acetate
Mixed liquor；PVA-KOH solution is mixed with glucose-red phosphorus-nickel acetate mixed liquor, stirs evenly, obtains mixed slurry；
Step 3: the mixed slurry that step 2 is obtained is coated on carbon fiber paper or PAN fiber film, coating thickness 10-
30um, fiber are covered by the mixed slurry completely, are then fed into tube furnace, made annealing treatment in argon atmosphere, annealing
After be washed with deionized, obtain carbon fiber/three-dimensional netted graphene composite material after dry.
In step 1, the mass ratio of PVA and KOH are (5~0): 1；The molecular weight of the PVA is 2000-300000.
In step 2, the mass ratio of glucose and red phosphorus is (5~0.1): 1, the quality of nickel acetate is the 5- of glucose quality
15%.
In step 2, when PVA-KOH solution is mixed with glucose-red phosphorus-nickel acetate mixed liquor, taken PVA-KOH solution
Quality is 10mg-50mg, and glucose-red phosphorus-nickel acetate mixed liquor quality is 5mg-25mg.
In step 3, the size of the carbon fiber paper or PAN fiber film is 1cm × 2cm, with a thickness of 30-150um.
In step 3, annealing temperature is 500-1200 DEG C, annealing time 1-10h, 1-20 DEG C of heating rate/min.
The application of carbon fiber prepared by the present invention/three-dimensional netted graphene composite material is with carbon fiber/three-dimensional netted stone
Negative electrode material of the black alkene composite material as supercapacitor.
The application of carbon fiber prepared by the present invention/three-dimensional netted graphene composite material is with two panels carbon fiber/three dimensional network
Shape graphene composite material is assembled into symmetry supercapacitor.
The application of carbon fiber prepared by the present invention/three-dimensional netted graphene composite material is by carbon fiber/three-dimensional netted stone
Black alkene composite material is as conductive substrates material, other electrode materials of further growth are on the conductive substrates material to prepare
Combination electrode material.Other described electrode materials include MnO2, NiO, PANI etc..
Carbon fiber prepared by the present invention/three-dimensional netted graphene composite material has tridimensional network, refers in carbon fiber
Growing three-dimensional porous graphene in dimension, the growth of graphene are connected to carbon fiber, form reticular structure.
The present invention provides graphene carbon source using the mixed slurry of preparation, while having pore-creating when sintering at high temperature and being thinned
Effect, so that the electrode material of preparation has high specific surface area and electric conductivity.Carbon fiber/three-dimensional of the method for the present invention preparation
Graphene net composite material forms integrated electron-transport path, enhancing while further increasing specific surface area
Its mechanical property.
The present invention using lower cost, it is simple, effectively, environmentally friendlyly prepare pattern and the stable carbon fiber/three dimensional network of performance
Shape graphene composite material has important development prospect.Can to carbon fiber of the present invention/three-dimensional netted graphene composite material into
The a variety of utilizations of row, such as directly as super capacitor anode material, or as flexible base material etc..Gained electrochemistry
The excellent electrode material of energy can be used in supercapacitor and other electrochemical energy storing devices.
The beneficial effects of the present invention are embodied in:
Preparation process of the present invention is simple, pollution-free, at low cost.Carbon fiber itself has that density is small, with high purity, mechanical strength
Height, the advantages such as stable chemical performance can be effectively improved its specific surface in grown on carbon fibers three-dimensional laminate structure graphene
Product shortens electron-transport path, to improve capacitive property.Carbon fiber paper itself is a kind of flexibility with good mechanical properties
Substrate can improve its electric conductivity, the flexible substrates as a kind of electrochemical performance are used in super after growing graphene
In capacitor, there is practice value.
Detailed description of the invention
Fig. 1 is carbon fiber/three-dimensional netted graphene composite material schematic diagram.
Fig. 2 is the carbon fiber/three-dimensional netted graphene composite material scanning electron microscope diagram piece prepared in embodiment.
From figure 2 it can be seen that in grown on carbon fibers 3D holey graphene.
Fig. 3 is the scanning electricity of graphene pattern in the carbon fiber/three-dimensional netted graphene composite material prepared in embodiment
Sub- microscope photograph.From figure 3, it can be seen that the graphene of growth has laminate structure, and there are many micropores, can shorten
Electronics and electrolyte ion transmission path.
Fig. 4 be in embodiment carbon fiber/three-dimensional netted graphene composite material for preparing in 1M H2SO4, three electrode assemblies
In chemical property.Wherein (a) is cyclic voltammetry curve of the composite material under different scanning rates；(b) speed is swept for difference
Under corresponding specific capacitance；It (c) is constant current charge-discharge curve of the composite material under different current densities；(d) close for different electric currents
Corresponding specific capacitance under degree.Figure 4, it is seen that prepared carbon fiber/three-dimensional netted graphene composite material is with good
Good chemical property, in acidic electrolysis bath, in 0.5Ag-1Under current density, specific capacitance reaches 160Fg-1.
Fig. 5 is that in three electrode assemblies, electric current is close for carbon fiber/three-dimensional netted graphene composite material for preparing in embodiment
Degree is 2A g-1When cycle performance.From figure 5 it can be seen that prepared carbon fiber/three-dimensional netted graphene composite material tool
There is good electrochemical stability, is 2Ag in current density-1, after 4000 times recycle, capacity retention 87%.
Fig. 6 is the chemical property of two panels carbon fiber/three-dimensional netted graphene composite material composition button cell.Wherein
It (a) is cyclic voltammetry curve of the battery under different scanning rates；(b) corresponding specific capacitance under speed is swept for difference；(c) battery exists
Constant current charge-discharge curve under different current densities；(d) corresponding specific capacitance under different current densities.From fig. 6 it can be seen that
The symmetric form supercapacitor of assembling has good chemical property, when not loading other active materials, than electricity
Appearance reaches 12Fg-1(being calculated based on positive and negative anodes carbon fiber/three-dimensional netted graphene composite material gross mass).
Fig. 7 is the carbon fiber/three-dimensional netted graphene composite material low power prepared in embodiment 2 and high power scanning electron
Microscope photograph.
Specific embodiment
Embodiment 1:
Carbon fiber/three-dimensional netted graphene composite material in the present embodiment the preparation method is as follows:
1, PVA solid (molecular weight=20000) 3g is weighed, 80 DEG C of stirring and dissolvings is warming up to after adding distilled water 30ml, obtains
PVA solution；KOH solid 1.5g is dissolved in 20ml distilled water, is then mixed with PVA solution, in 70 DEG C of stirring 10min, is obtained
Obtain PVA-KOH solution；
2, glucose powder 1g, red phosphorus 1g and nickel acetate 0.05g are weighed, 30ml distilled water is added, is stirred at 70 DEG C
5h, until solution in thick, obtains glucose-red phosphorus-nickel acetate mixed liquor；PVA-KOH solution 10mL that step 1 is obtained with
Glucose-red phosphorus that this step obtains-nickel acetate mixed liquor 10mL mixing, stirs evenly, obtains mixed slurry；
3, the mixed slurry for obtaining step 2 is coated on carbon fiber paper or PAN fiber film (thick having a size of 1cm × 2cm
Degree is 30um), the coated weight of mixed slurry is 3mL, is then fed into tube furnace, is made annealing treatment in an ar atmosphere, is annealed
Temperature is 750 DEG C, annealing time 5h, 2 DEG C/min of heating rate；It is washed with deionized after annealing, obtains carbon fiber after dry
Dimension/three-dimensional netted graphene composite material.Its schematic diagram such as Fig. 1, the three-dimensional netted graphene of grown on carbon fibers, and formed porous
Structure.
4, electrochemical property test is carried out to carbon fiber obtained/three-dimensional netted graphene composite material, with platinized platinum
To be reference electrode, 1M H to electrode, Ag/AgCl2SO4It is carried out in the three-electrode system of electrolyte.Test method includes circulation volt
An Fa, constant current charge-discharge test and cyclical stability test.
Carbon fiber made from the present embodiment/three-dimensional netted graphene composite material, as shown in Fig. 2, there is porous structure, easily
In the transmission of electronics and ion, the graphene and carbon fiber to interlink has good mechanical performance.Carbon fiber/three dimensional network
Shape graphene composite material compares simple carbon fiber, and electric conductivity improves, while thin graphene (Fig. 3) structure has higher ratio
Surface area can improve electrode material capacitive property.In three-electrode system, 1M H2SO4Good electrification is obtained in electrolyte
Learn performance, including high specific capacitance as shown in figure 4, and good cyclical stability it is as shown in Figure 5.And two panels carbon fiber can be used
Dimension/Graphene electrodes, general fibre element paper are diaphragm, and 2M KOH is that electrolyte is assembled into button cell, are led not adding other
Considerable chemical property is obtained under electric substrate and active electrode material, under the biggish window of 1.4V, can be carried out constant current and be filled
Discharge test, as shown in Figure 6.
Embodiment 2:
Carbon fiber/three-dimensional netted graphene composite material in the present embodiment the preparation method is as follows:
1, KOH solid 1.5g is weighed, 30ml distilled water is added, stirring and dissolving on magnetic stirring apparatus is placed in and obtains KOH solution；
2,3g glucose, 0.6g nickel acetate, 0.8g red phosphorus are weighed respectively, and the mixing of 20mL distilled water is added, stirs at 80 DEG C
It is in thick for mixing to solution, obtains glucose-red phosphorus-nickel acetate mixed liquor；The KOH solution 10mL that step 1 is obtained and this step
Suddenly glucose-the red phosphorus obtained-nickel acetate mixed liquor 10mL mixing, stirs evenly, obtains mixed slurry；
3, the mixed slurry for obtaining step 2 is coated on carbon fiber paper (having a size of 1cm × 1cm, with a thickness of 30um), is mixed
The coated weight for closing slurry is 3mL, is spontaneously dried overnight；It is then fed into tube furnace, is made annealing treatment in argon atmosphere, moved back
Fiery temperature is 750 DEG C, annealing time 5h, 2 DEG C/min of heating rate；It is washed with deionized after annealing, obtains carbon after dry
Fiber/three-dimensional netted graphene composite material.Its schematic diagram is as shown in fig. 7, the three-dimensional netted graphene of grown on carbon fibers, and shape
At porous structure.
Claims (9)
1. a kind of carbon fiber/three-dimensional netted graphene composite material preparation method, it is characterised in that include the following steps:
Step 1: weighing PVA 0~6g of solid, be warming up to 70-90 DEG C of stirring and dissolving after adding distilled water 30ml, obtain PVA solution；It will
KOH solid is dissolved in 10-30ml distilled water, is then mixed with PVA solution, in 60-80 DEG C of stirring 10-300min, is obtained
PVA-KOH solution or KOH solution；
Step 2: weighing 0.1~5g of glucose powder, 0.01~1g of 0.01~1.5g of red phosphorus and nickel acetate, 20-30ml is added
Distilled water mixing, stirs 10-300min at 50-80 DEG C, until solution in thick, obtains glucose-red phosphorus-nickel acetate mixing
Liquid；PVA-KOH solution or KOH solution that step 1 obtains are mixed with glucose-red phosphorus-nickel acetate mixed liquor, stirred evenly,
Obtain mixed slurry；
Step 3: the mixed slurry that step 2 is obtained is coated on carbon fiber paper or PAN fiber film, and coating thickness is 10-30 μm,
It is then fed into tube furnace, is made annealing treatment in argon atmosphere, is washed with deionized after annealing, obtain carbon fiber after dry
Dimension/three-dimensional netted graphene composite material.
2. preparation method according to claim 1, it is characterised in that:
In step 1, the mass ratio of PVA and KOH are (5~0): 1；The molecular weight of the PVA is 2000-300000.
3. preparation method according to claim 1, it is characterised in that:
In step 2, the mass ratio of glucose and red phosphorus is (5~0.1): 1, the quality of nickel acetate is the 5- of glucose quality
15%.
4. preparation method according to claim 1, it is characterised in that:
In step 2, when PVA-KOH solution or KOH solution are mixed with glucose-red phosphorus-nickel acetate mixed liquor, taken PVA-KOH
The quality of solution or KOH solution is 10mg-50mg, and glucose-red phosphorus-nickel acetate mixed liquor quality is 5mg-25mg.
5. preparation method according to claim 1, it is characterised in that:
In step 3, the size of the carbon fiber paper or PAN fiber film is 1cm × 2cm, with a thickness of 30-150 μm.
6. preparation method according to claim 1, it is characterised in that:
In step 3, annealing temperature is 500-1200 DEG C, annealing time 1-10h, 1-20 DEG C of heating rate/min.
7. a kind of carbon fiber/three-dimensional netted graphene composite material application of preparation method preparation described in claim 1,
It is characterized in that:
It is the negative electrode material using carbon fiber/three-dimensional netted graphene composite material as supercapacitor.
8. a kind of carbon fiber/three-dimensional netted graphene composite material application of preparation method preparation described in claim 1,
It is characterized in that:
It is that symmetry supercapacitor is assembled into two panels carbon fiber/three-dimensional netted graphene composite material.
9. a kind of carbon fiber/three-dimensional netted graphene composite material application of preparation method preparation described in claim 1,
It is characterized in that:
Be using carbon fiber/three-dimensional netted graphene composite material as conductive substrates material, it is enterprising in the conductive substrates material
Other electrode materials of one step growth are to prepare combination electrode material.
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Inventor after: Yan Jian Inventor after: Wang Weijie Inventor after: Ou Dawei Inventor after: Qin Qingqing Inventor after: Wu Yucheng Inventor before: Yan Jian Inventor before: Ou Dawei Inventor before: Wang Weijie Inventor before: Qin Qingqing Inventor before: Wu Yucheng |
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Effective date of registration: 20230920 Address after: Room 715, Building B, Hongqiao World Center, Lane 1588 Zhuguang Road, Xujing Town, Qingpu District, Shanghai, 201702 Patentee after: Shanghai Gesu Electronic Technology Co.,Ltd. Address before: Tunxi road in Baohe District of Hefei city of Anhui Province, No. 193 230009 Patentee before: Hefei University of Technology |