CN107010615A - A kind of preparation method and applications of three-dimensional grapheme - Google Patents
A kind of preparation method and applications of three-dimensional grapheme Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and applications of three-dimensional grapheme, this method is after oxygen-containing organic polymer is mixed with mantoquita, to be placed in indifferent gas atmosphere and calcine, and calcined product is washed by liquor ferri trichloridi, dried, and produces three-dimensional grapheme；This method is simple to operate just, the cycle is short, and yield is high, is conducive to industrialized production；Obtained three-dimensional grapheme material, can be used as sodium ion battery electrode material, and with excellent chemical property.
Description
Technical field
The present invention relates to a kind of preparation method of three-dimensional grapheme material, more particularly to using copper salt with it is oxygen-containing organic
Polymer prepares the method for three-dimensional grapheme and its application in sodium-ion battery, belongs to the system of sodium ion battery electrode material
Standby technical field.
Background technology
Graphene is by sp2Carbon atom connects to form two-dimensional sheet structure, carbon atom it is regular be arranged in honeycomb lattice
It is most thin one kind in known materials among construction unit.As simple substance, the electron transmission speed of graphene can reach
15000cm2/ Vs, surmounts known all conductors.Have benefited from the special Atomic Arrangement of graphene itself, the tension of the material is strong
Degree can reach 125GPa, and the modulus of elasticity of the material is 1.1TPa.A kind of graphene also excellent heat conductor,
Its carrier density is relatively low, and conducts heat and rely primarily in phonon propagation, and thermal conductivity factor is up to 5*103W/m K, in addition, all
The interphase interaction of carbon atom, forms the big pi bond of delocalization, electronics can move freely in this region so that the electrical conductivity of material is
106S/m, higher electrical conductivity causes material to have very high development prospect in energy storage field.
However, Van der Waals interaction strong between graphene, causes uniform monodispersed graphene easily to be sent out
Raw agglomeration.Have a strong impact on the mechanical properties strength of grapheme material, high rate of heat transfer, the advantage such as high conductance,
Grapheme material is prevented in the energy, biological, the field such as environment is further used.Built by graphene laminated structure three-dimensional
Network structure, effectively alleviates the agglomeration of grapheme material, it is to avoid the repeating of single graphene sheet layer, and this is right
In maintaining, the bulk properties of grapheme material are particularly significant.Three-dimensional grapheme builds the means for being considered as maximally efficient and promotes graphite
The development of alkene, people are directed to developing new three-dimensional grapheme network structure always.
The preparation method of traditional three-dimensional grapheme is divided into mechanical stripping method, and epitaxial growth method, chemical vapour deposition technique is changed
Learn stripping method etc., although but mechanical stripping method can synthesize the higher three-dimensional grapheme of purity, but larger, the yield that consumes energy
It is smaller.And epitaxial growth method and chemical gas-phase method, although can be with the excellent three-dimensional grapheme material of synthesis performance, but produce work
Skill is complicated, and cost is larger, is not appropriate for the large-scale production of material.And the synthetic method of chemical stripping, more will use
The chemical reagent of poison, prevents the commercialization of this method.
The content of the invention
The defect existed for the existing method for preparing three-dimensional grapheme material, it is an object of the invention to be to carry
For a kind of raw material sources are wide, step and the simple to operate, cycle is short, yield the is high method for preparing three-dimensional grapheme.
Another object of the present invention is to be to provide a kind of application of the three-dimensional grapheme, and three-dimensional grapheme has three
Network architecture is tieed up, is on the one hand conducive to the infiltration of electrolyte, and forms three-dimensional conductive network structure, with preferable electrification
Activity is learned, sodium-ion battery is used it for, with excellent properties such as high power capacity, high power, long-lives.
In order to realize above-mentioned technical purpose, the invention provides a kind of preparation method of three-dimensional grapheme, this method be by
After oxygen-containing organic polymer is mixed with mantoquita, it is placed in indifferent gas atmosphere, is calcined at a temperature of 400~800 DEG C, calcining production
Thing is washed by liquor ferri trichloridi, dried, and is produced.
It is preferred that scheme, the mass ratio of oxygen-containing organic polymer and mantoquita is 1:1~20.More preferably ratio is 1:1~
10.Most preferably 1:5~10.If mantoquita ratio is too low, cause during three-dimensional grapheme is generated, template is not enough,
In turn resulting in the three-dimensional structure of material can not generate.And mantoquita is excessive, the waste of resource can be caused, to the pattern of three-dimensional grapheme
Influence is little.
More preferably scheme, the oxygen-containing organic polymer be selected from carbon quantum dot, polyethylene glycol, polyvinyl alcohol, polyformaldehyde,
PEO, epoxy resin, makrolon, PolyTHF, polyphenylene oxide, polyvinyl formal, polyacrylic acid, polyacetals tree
At least one of fat, resorcinol formaldehyde resin, phenolic resin.More preferably carbon quantum dot, polyethylene glycol, polyvinyl alcohol, phenol
At least one of urea formaldehyde.More preferably carbon quantum dot.It is preferred that oxygen-containing organic polymer in be rich in oxygen, in carbonization, graphitization
During be easier with copper act on, aggregation assembling form three-dimensional network frame structure.Simultaneously can be right using oxygen-containing organic polymer
Three-dimensional grapheme material carries out appropriate oxygen doping, to improve the chemical property of three-dimensional grapheme.
More preferably scheme, the mantoquita be selected from stannous chloride, copper chloride, copper acetate, copper sulphate, copper carbonate, cupric phosphate,
At least one of copper nitrate, hydrogen phosphite copper.More preferably at least one in stannous chloride, copper chloride, copper acetate, copper nitrate
Kind.
It is preferred that scheme, calcining heat be 600~700 DEG C.
More preferably scheme, calcination time is 0.5h~10h；Preferably 2~5h.
Heating rate in more preferably scheme, calcination process is 1~15 DEG C/min；More preferably 5~10 DEG C/min.
Present invention also offers the application of three-dimensional grapheme, sodium-ion battery is applied to as electrode material.
It is preferred that scheme, three-dimensional grapheme mixed with binding agent and conductive black by rubbing method is coated on electrode slice make
Standby electrode.
It is preferred that scheme, the mass ratio of three-dimensional grapheme and binding agent and conductive black is 65~75:10~15:15~
20。
Three-dimensional grapheme is impregnated or washed using liquor ferri trichloridi in technical scheme, it is therefore an objective to
The compositions such as the copper gone out in graphene.Cleaning solution or maceration extract reclaim mantoquita by the mode such as concentration, dry, reuse.
Mixing is generally referred to as conventional mechanical mixture in technical scheme, such as mills.
Inert atmosphere refers to helium, argon gas, nitrogen etc. in technical scheme, can be their gaseous mixture
Atmosphere.
Technical scheme mixes mantoquita with oxygen-containing organic polymer, with the oxygen-containing organic polymer of the rising of temperature
Thing is gradually polymerize on the surface of mantoquita mantoquita is coated in, raised with the continuation of temperature, the copper simple substance particle of generation
The effect of template and framework is served in the inside of oxygen-containing organic polymer, oxygen-containing organic polymer is by carbonization, graphitization, structure
Three-dimensional network frame structure is built up, copper mold plate is removed by using liquor ferri trichloridi washing, just generates three-dimensional grapheme structure.
Compared with the prior art, the advantageous effects that technical scheme is brought：
1st, technical scheme is using mantoquita and oxygen-containing organic polymer as raw material, using being simply mixed, calcine and wash
Wash process combination, you can to obtain three-dimensional grapheme, this method yield is high, and technological process is short, and the cycle is short, and production efficiency is obtained greatly
Big to improve, the relatively existing technology for preparing three-dimensional grapheme enormously simplify processing step, be conducive to industrialized production.
2nd, three-dimensional grapheme prepared by technical scheme has stable porous three-dimensional frame structure, porous knot
Structure, is conducive to ion to transmit, and three-dimensional box framework stability in charge and discharge process is good；It is particularly well suited as sodium-ion battery
Electrode material is used, and can be effectively improved and be received capacity, the power of ion battery, increase the service life.
3rd, the raw material that technical scheme is used is simple, and source is wide, and cost is low, and copper salt can be recycled
Use, substantially reduce use cost.
Brief description of the drawings
【Fig. 1】It is the stereoscan photograph of the three-dimensional grapheme obtained in embodiment 1；
【Fig. 2】It is the transmission electron microscope photo of the three-dimensional grapheme obtained in embodiment 1；
【Fig. 3】It is the XRD spectra of the three-dimensional grapheme obtained in embodiment 1；
【Fig. 4】It is the stereoscan photograph of the three-dimensional grapheme obtained in embodiment 2；
【Fig. 5】It is the transmission electron microscope photo of the three-dimensional grapheme obtained in embodiment 2；
【Fig. 6】It is the stereoscan photograph of the three-dimensional grapheme obtained in embodiment 3；
【Fig. 7】It is the transmission electron microscope photo of the three-dimensional grapheme obtained in embodiment 3；
【Fig. 8】It is the stereoscan photograph of the three-dimensional grapheme obtained in embodiment 4；
【Fig. 9】It is the transmission electron microscope photo of the three-dimensional grapheme obtained in embodiment 4；
【Figure 10】It is the block structure stereoscan photograph obtained in comparative example 2；
【Figure 11】It is the block structure stereoscan photograph obtained in comparative example 3；
【Figure 12】It is high rate performance of the battery assembled in embodiment 1 under different current densities.
Embodiment
Following examples are that, in order to which the present invention is explained in greater detail, these embodiments do not constitute any limitation to the present invention,
The present invention can be as described in the content of the invention either type implement.
Embodiment 1
0.4g carbon quantum dots and 4.0g stannous chlorides are well mixed, then by it under Ar gas shields, 700 DEG C of calcinings
5h, heating rate is 10 DEG C/min, Temperature fall.By the product grind into powder after calcining, excessive ferric trichloride is added molten
Liquid, its pH is adjusted to neutrality, and 10min is centrifuged under 10000r/min rotating speeds, is cleaned with deionized water 5 times, at 100 DEG C
12h is dried in vacuo, black powder 0.15g is obtained.Its scanning electron microscopic picture is Fig. 1, it can be seen that product is three-dimensional grapheme knot
Structure.Fig. 2 is its transmission electron microscope picture, consistent with ESEM result.Fig. 3 is its X-ray diffraction spectrogram, and obtained product is graphite
Olefinic carbon.
By obtained three-dimensional grapheme carbon material, sodium carboxymethylcellulose, conductive black in mass ratio 70:15:15 mixing
Uniformly, add appropriate ultra-pure water slurry is made and is applied on copper foil, dried after being placed in after water volatilization in vacuum drying chamber at 100 DEG C
The copper foil for scribbling active material, is then cut into diameter 13mm disk by 12h.To scribble a diameter of 13mm of active material
Disk is working electrode, and metallic sodium is that, to electrode, Celgard2400 composite membranes are barrier film, are assembled in inert atmosphere glove box
Button cell.Electrochemical property test shows that obtained three-dimensional grapheme has excellent circulation performance, 0.5,1,2,
4、10Ag-1Current density under, reversible specific capacity is respectively 215.3,185.9,144..3,113.2,73mAh g-1, and in warp
After super-high-current circulation, when current density returns to 0.5Ag-1Afterwards, reversible specific capacity can return to 208.5mAh g-1。
Embodiment 2
0.4g PEG-6000 and 4.0g stannous chlorides are well mixed, then by it under Ar gas shields, 700 DEG C are forged
4h is burnt, heating rate is 10 DEG C/min, Temperature fall.By the product grind into powder after calcining, excessive ferric trichloride is added
Solution, its pH is adjusted to neutrality, and 10min is centrifuged under 10000r/min rotating speeds, is cleaned with deionized water 5 times, at 100 DEG C
Lower vacuum drying 12h, obtains black powder 0.14g.Its scanning electron microscopic picture is Fig. 4, it can be seen that product is three-dimensional grapheme
Structure.Fig. 5 is its transmission electron microscope picture, consistent with ESEM result.
By obtained three-dimensional grapheme carbon material, sodium carboxymethylcellulose, conductive black in mass ratio 70:15:15 mixing
Uniformly, add appropriate ultra-pure water slurry is made and is applied on copper foil, dried after being placed in after water volatilization in vacuum drying chamber at 100 DEG C
The copper foil for scribbling active material, is then cut into diameter 13mm disk by 12h.To scribble a diameter of 13mm of active material
Disk is working electrode, and metallic sodium is that, to electrode, Celgard2400 composite membranes are barrier film, are assembled in inert atmosphere glove box
Button cell.Electrochemical property test shows that obtained three-dimensional grapheme has excellent cycle performance, in 0.1A g-1Electricity
Under current density, after the circulation for entering 100 cycles, the specific discharge capacity of material remains unchanged and can maintain 255.7mAh g-1, exhibition
Splendid cyclical stability is revealed.
Embodiment 3
0.4g carbon quantum dots and 2.0g stannous chlorides are well mixed, then by it in N2Under gas shield, 750 DEG C of calcinings
5h, heating rate is 8 DEG C/min, Temperature fall.By the product grind into powder after calcining, excessive ferric trichloride is added molten
10min is centrifuged under liquid, 10000r/min rotating speeds, is cleaned with deionized water 5 times, 12h is dried in vacuo at 100 DEG C, obtains
Black powder 0.14g.Its scanning electron microscopic picture is Fig. 6, it can be seen that product is three-dimensional grapheme structure.Fig. 7 is its transmission electricity
Mirror figure, it is consistent with ESEM result.
By obtained three-dimensional grapheme carbon material, sodium carboxymethylcellulose, conductive black in mass ratio 70:15:15 mixing
Uniformly, add appropriate ultra-pure water slurry is made and is applied on copper foil, dried after being placed in after water volatilization in vacuum drying chamber at 100 DEG C
The copper foil for scribbling active material, is then cut into diameter 13mm disk by 12h.To scribble a diameter of 13mm of active material
Disk is working electrode, and metallic sodium is that, to electrode, Celgard2400 composite membranes are barrier film, are assembled in inert atmosphere glove box
Button cell.Electrochemical property test shows that obtained three-dimensional grapheme has excellent cycle performance, in 0.1Ag-1Electric current
Under density, after the circulation for entering 100 cycles, the specific discharge capacity of material remains unchanged and can maintain 247.9mAh g-1, and
Coulombic efficiency can reach 99.6%, show splendid cyclical stability.
Embodiment 4
0.4g polyacrylic acid and 4.0g copper nitrates are well mixed, then by it under Ar gas shields, 800 DEG C of calcinings
5h, heating rate is 10 DEG C/min, Temperature fall.By the product grind into powder after calcining, excessive ferric trichloride is added molten
10min is centrifuged under liquid, 10000r/min rotating speeds, is cleaned with deionized water 5 times, 12h is dried in vacuo at 100 DEG C, obtains
Black powder 0.13g.Its scanning electron microscopic picture is Fig. 8, it can be seen that product is three-dimensional grapheme structure.Fig. 9 is its transmission electricity
Mirror figure, it is consistent with ESEM result.
By obtained three-dimensional grapheme carbon material, sodium carboxymethylcellulose, conductive black in mass ratio 70:15:15 mixing
Uniformly, add appropriate ultra-pure water slurry is made and is applied on copper foil, dried after being placed in after water volatilization in vacuum drying chamber at 100 DEG C
The copper foil for scribbling active material, is then cut into diameter 13mm disk by 12h.To scribble a diameter of 13mm of active material
Disk is working electrode, and metallic sodium is that, to electrode, Celgard2400 composite membranes are barrier film, are assembled in inert atmosphere glove box
Button cell.Electrochemical property test shows that obtained three-dimensional grapheme has excellent cycle performance, in 0.1Ag-1Electric current
Under density, after the circulation for entering 100 cycles, the specific discharge capacity of material remains unchanged and can maintain 233.5mAh g-1, and
Coulombic efficiency can reach 99.4%, show splendid cyclical stability.
Embodiment 5
0.4g polyethylene glycol -12000 and 4.0g copper acetates are well mixed, then by it under Ar gas shields, 600 DEG C
5h is calcined, heating rate is 10 DEG C/min, Temperature fall.By the product grind into powder after calcining, excessive tri-chlorination is added
10min is centrifuged under ferrous solution, 10000r/min rotating speeds, is cleaned with deionized water 5 times, 12h is dried in vacuo at 100 DEG C,
Obtain black powder.
By obtained three-dimensional grapheme carbon material, sodium carboxymethylcellulose, conductive black in mass ratio 70:15:15 mixing
Uniformly, add appropriate ultra-pure water slurry is made and is applied on copper foil, dried after being placed in after water volatilization in vacuum drying chamber at 100 DEG C
The copper foil for scribbling active material, is then cut into diameter 13mm disk by 12h.To scribble a diameter of 13mm of active material
Disk is working electrode, and metallic sodium is that, to electrode, Celgard2400 composite membranes are barrier film, are assembled in inert atmosphere glove box
Button cell.Electrochemical property test shows that obtained three-dimensional grapheme has excellent cycle performance, in 0.2Ag-1Electric current
Under density, after the circulation for entering 200 cycles, the specific discharge capacity of material remains unchanged and can maintain 213.1mAh g-1, and
Coulombic efficiency can reach 99.0%, show splendid cyclical stability.
Embodiment 6
0.4g carbon quantum dots and 4.0g stannous chlorides are well mixed, then by it under Ar gas shields, 800 DEG C of calcinings
5h, heating rate is 5 DEG C/min, Temperature fall.By the excessive liquor ferri trichloridi of the product grind into powder after calcining,
10min is centrifuged under 10000r/min rotating speeds, is cleaned with deionized water 5 times, 12h is dried in vacuo at 100 DEG C, obtains black
Powder.
By obtained three-dimensional grapheme carbon material, sodium carboxymethylcellulose, conductive black in mass ratio 70:15:15 mixing
Uniformly, add appropriate ultra-pure water slurry is made and is applied on copper foil, dried after being placed in after water volatilization in vacuum drying chamber at 100 DEG C
The copper foil for scribbling active material, is then cut into diameter 13mm disk by 12h.To scribble a diameter of 13mm of active material
Disk is working electrode, and metallic sodium is that, to electrode, Celgard2400 composite membranes are barrier film, are assembled in inert atmosphere glove box
Button cell.Electrochemical property test shows that obtained three-dimensional grapheme has excellent cycle performance, in 1.0Ag-1Electric current
Under density, after the circulation for entering 100 cycles, the specific discharge capacity of material remains unchanged and can maintain 155.7mAh g-1, and
Coulombic efficiency can reach 98.0%, show splendid cyclical stability.
Comparative example 1
0.4g carbon quantum dots and 4.0g stannous chlorides are well mixed, then by it under Ar gas shields, 900 DEG C of calcinings
5h, heating rate is 5 DEG C/min, Temperature fall.By the product grind into powder after calcining, excessive liquor ferri trichloridi, this
When solution show transparent brown color, the not solid matter of black, this point can illustrate, in the higher situation of temperature
Under, three-dimensional grapheme material can not be generated.
Comparative example 2
0.4g carbon quantum dots and 4.0g stannous chlorides are well mixed, then by it under Ar gas shields, 300 DEG C of calcinings
5h, heating rate is 5 DEG C/min, Temperature fall.By the excessive liquor ferri trichloridi of the product grind into powder after calcining,
10min is centrifuged under 10000r/min rotating speeds, is cleaned with deionized water 5 times, 12h is dried in vacuo at 100 DEG C, obtains black
Powder.Its scanning electron microscopic picture is Figure 10, it can be seen that product is block structure, and this is probably because carbon quantum dot is not sent out also
Raw carbonization.
Comparative example 3
0.4g carbon quantum dots and 0.1g stannous chlorides are well mixed, then by it under Ar gas shields, 700 DEG C of calcinings
5h, heating rate is 10 DEG C/min, Temperature fall.By the excessive liquor ferri trichloridi of the product grind into powder after calcining,
10min is centrifuged under 10000r/min rotating speeds, is cleaned with deionized water 5 times, 12h is dried in vacuo at 100 DEG C, obtains black
Powder.Its scanning electron microscopic picture is Figure 11, it can be seen that product is block structure, the missing of template, and simply material can not give birth to
Into complete three-dimensional structure.
Claims (10)
1. a kind of preparation method of three-dimensional grapheme, it is characterised in that：After oxygen-containing organic polymer is mixed with mantoquita, it is placed in lazy
Property atmosphere enclose, calcined at a temperature of 400~800 DEG C, calcined product by liquor ferri trichloridi washing, dry, produce.
2. the preparation method of three-dimensional grapheme according to claim 1, it is characterised in that：Oxygen-containing organic polymer and mantoquita
Mass ratio be 1:1~20.
3. the preparation method of three-dimensional grapheme according to claim 2, it is characterised in that：The oxygen-containing organic polymer choosing
From carbon quantum dot, polyethylene glycol, polyvinyl alcohol, polyformaldehyde, PEO, epoxy resin, makrolon, PolyTHF,
At least one of polyphenylene oxide, polyvinyl formal, polyacrylic acid, aldehyde resin, resorcinol formaldehyde resin, phenolic resin.
4. the preparation method of three-dimensional grapheme according to claim 2, it is characterised in that：The mantoquita is selected from protochloride
At least one of copper, copper chloride, copper acetate, copper sulphate, copper carbonate, cupric phosphate, copper nitrate, hydrogen phosphite copper.
5. the preparation method of the three-dimensional grapheme according to any one of Claims 1 to 4, it is characterised in that：Calcining heat is
600~700 DEG C.
6. the preparation method of three-dimensional grapheme according to claim 5, it is characterised in that：Calcination time is 0.5h~10h.
7. the preparation method of the three-dimensional grapheme according to any one of Claims 1 to 4, it is characterised in that：In calcination process
Heating rate be 1~15 DEG C/min.
8. the application of three-dimensional grapheme prepared by the preparation method described in any one of claim 1~7, it is characterised in that：As
Electrode material is applied to sodium-ion battery.
9. the application of three-dimensional grapheme according to claim 8, it is characterised in that：Three-dimensional grapheme and binding agent and conduction
Carbon black mixing is coated on electrode slice by rubbing method prepares electrode.
10. the application of three-dimensional grapheme according to claim 9, it is characterised in that：Three-dimensional grapheme and binding agent and lead
The mass ratio of electric carbon black is 65~75:10~15:15~20.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111470494A (en) * | 2020-04-10 | 2020-07-31 | 广东工业大学 | Preparation method and application of three-dimensional graphene |
| CN113471427A (en) * | 2021-05-20 | 2021-10-01 | 福建海峡石墨烯产业技术研究院有限公司 | Carbon quantum dot and graphene composite material and preparation method and application thereof |
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