CN105047425B - A kind of preparation method of graphene/Spherical Carbon/metal oxide composite - Google Patents
A kind of preparation method of graphene/Spherical Carbon/metal oxide composite Download PDFInfo
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- CN105047425B CN105047425B CN201510375421.7A CN201510375421A CN105047425B CN 105047425 B CN105047425 B CN 105047425B CN 201510375421 A CN201510375421 A CN 201510375421A CN 105047425 B CN105047425 B CN 105047425B
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Abstract
The invention discloses a kind of preparation method of graphene/Spherical Carbon/metal oxide composite, including step once：Weigh by mass percentage：Resorcinol solution or quinol solution 8%~20%, formalin or furfuryl aldehyde solution 5%~10%, distilled water 65%~80%, graphene suspension 3%~8%, catalyst 4% 10%, the content summation of above component is 100%；Well mixed be made of above-mentioned raw materials is reacted into initial liquid；React initial liquid to move into the vial with seal closure, cover bottle cap and be placed in gel reaction in drying box, gel is made；Salting liquid is first added dropwise to saturation in wet gel again through drying process, and alkaline solution is added dropwise after drying again to saturation, is made after carbonization.The composite of graphene/Spherical Carbon/metal oxide produced by the present invention has high specific surface area, possesses electric double layer capacitance, has higher specific capacitance and efficiency for charge-discharge, improves the electric conductivity of electrode, disclosure satisfy that high-power power demands.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, is related to a kind of graphene/Spherical Carbon/metal oxide composite wood
The preparation method of material.
Background technology
Nano-carbon material using CNT, graphene and carbon nano-fiber as representative, because its high-specific surface area, height are led
Electrical and intrinsic carbon material stability, it is the study hotspot in current new energy materialses field.Nano-sized carbon is answered with metal oxide
Composite electrode materials application can significantly improve specific capacitance, specific power, specific capacity and the charge and discharge of ultracapacitor in ultracapacitor
Electrical efficiency.But prepared by existing nano-carbon material need high temperature or overcritical or freeze-drying, cost height is prepared, and exist
The problem of specific capacitance, relatively low specific power, limit electrode material should be in scope.
The content of the invention
It is an object of the invention to provide a kind of preparation method of graphene/Spherical Carbon/metal oxide composite, solves
The problem of needing high temperature, overcritical or freeze-drying etc. to be required compared with high technology existing for existing nano carbon material preparation method for material.
The technical scheme is that a kind of preparation method of graphene/Spherical Carbon/metal oxide composite, tool
Body is real according to following steps：
Step 1, weigh by mass percentage：Resorcinol solution or quinol solution 8%~20%, formalin or
Furfuryl aldehyde solution 5%~10%, distilled water 65%~80%, graphene suspension 3%~8%, catalyst 4%~10%, the above
The content summation of component is 100%；
Step 2, by the resorcinol solution weighed through step 1 or quinol solution, formalin or furfuryl aldehyde solution, stone
Black alkene suspension and catalyst are added in the distilled water weighed through step 1, stir, and the initial liquid of reaction is made；
Step 3, will be moved into through the obtained initial liquid of reaction of step 2 in the vial with seal closure, cover bottle cap be placed in it is dry
Gel reaction processing is carried out in dry case, wet gel is made；
Step 4, processing will be dried through wet gel made from step 3, and obtain desiccant gel；
Step 5, the salting liquid that configuration quality concentration is 25%~35%, instill desiccant gel by salting liquid, are added dropwise dropwise
Measure as 4-5 times of desiccant gel volume, be then placed in drying box and fully dry, wherein salting liquid is CoCl2·6H2O、NiCl2·
2H2O、CuCl2·2H2O or ZnAc2H2O solution；
Step 6, repeat step more than 5 times, untill gel saturation；
Step 7, alkaline solution is instilled to the desiccant gel handled through step 6 dropwise, be put into drying box and fully dry, wherein
Alkaline solution is NaOH solution, KOH solution or the ammoniacal liquor of mass concentration 35%~45%；
Step 8, the desiccant gel handled through step 7 is carried out to carbonization treatment, obtained graphene/Spherical Carbon/metal oxidation
The specific implementation method of thing composite, wherein carbonization treatment is：Using the tube furnace of both ends open, by 40cc~60cc flows
The nitrogen of air or purity not less than 99.999% is passed through, 650 DEG C~700 are warming up to according to 10 DEG C~50 DEG C speed per minute
DEG C and be incubated 2~4 hours, Temperature fall.
The features of the present invention also resides in,
In step 1, the mass concentration of resorcinol solution or quinol solution are 10%~50%；Formalin or chaff
The mass concentration of aldehyde solution is 10%~50%；Graphene-containing 10mg~15mg in every liter of graphene suspension；Catalyst is
CoCl2·6H2O、NiCl2·2H2O、CuCl2·2H2O or ZnAc2H2O。
In step 2, stirring means are magnetic agitation, 2~3h of mixing time.
In step 3, gel reaction temperature is 80 DEG C~95 DEG C, and the gel reaction time is 30min~60min.
In step 4, the specific implementation method of drying process is：Obtained wet gel is positioned over 80 DEG C~100 DEG C dry
Dried 1~3 hour in dry case.
The invention has the advantages that a kind of preparation method of graphene/Spherical Carbon/metal oxide composite, leads to
Cross in-situ method and prepare three-dimensional porous structure material, then by multiple infusion method, graphene/spherical nanocarbon/metal is obtained after carbonization
The super capacitor material of the composite of oxide-i.e., has high specific surface area, so as to possess electric double layer capacitance, metal oxygen
The redox reaction of compound is appraised at the current rate and possesses fake capacitance, the two synergy, obtains higher specific capacitance and efficiency for charge-discharge,
The electric conductivity of electrode is improved, disclosure satisfy that high-power power demands.
Brief description of the drawings
Fig. 1 is graphene/Spherical Carbon/metal oxide composite stereoscan photograph prepared by the present invention；
Fig. 2 is the transmission electron microscope photo of graphene/Spherical Carbon/metal oxide composite prepared by the present invention；
Fig. 3 is the electrochemical properties figure of graphene/Spherical Carbon/metal oxide composite prepared by the present invention.
Embodiment
With reference to embodiment, the present invention is described in detail.
A kind of preparation method of graphene/Spherical Carbon/metal oxide composite of the present invention, specifically according to following steps
Implement：
Step 1, weigh by mass percentage：Resorcinol solution or quinol solution 8%~20%, formalin or
Furfuryl aldehyde solution 5%~10%, distilled water 65%~80%, graphene suspension 3%~8%, catalyst 4%~10%, the above
The content summation of component is 100%；Wherein, the mass concentration of resorcinol solution or quinol solution are 10%~50%；
Formalin or the mass concentration of furfuryl aldehyde solution are 10%~50%；Graphene-containing 10mg in every liter of graphene suspension~
15mg；Catalyst is CoCl2·6H2O、NiCl2·2H2O、CuCl2·2H2O or ZnAc2H2O；
Step 2, by the resorcinol solution weighed through step 1 or quinol solution, formalin or furfuryl aldehyde solution, stone
Black alkene suspension and catalyst are added in the distilled water weighed through step 1, magnetic agitation 2h~3h, and the initial liquid of reaction is made；
Step 3, will be moved into through the obtained initial liquid of reaction of step 2 in the vial with seal closure, cover bottle cap be placed in it is dry
Gel reaction processing is carried out in dry case, gel reaction temperature is 80 DEG C~95 DEG C, and the gel reaction time is 30min~60min, system
Obtain wet gel；
Step 4, processing will be dried through wet gel made from step 3, obtained wet gel is positioned over 80 DEG C~100
DEG C drying box in dry 1~3 hour, obtain desiccant gel；
Step 5, the salting liquid that configuration quality concentration is 25%~35%, wherein, salting liquid CoCl2·6H2O、
NiCl2·2H2O、CuCl2·2H2O or ZnAc2H2O solution, salting liquid is instilled into desiccant gel dropwise, dripping quantity is 4-5 times
Desiccant gel volume, it is then placed in drying box and fully dries；
Step 6, repeat step more than 5 times, untill gel saturation；
Step 7, alkaline solution is instilled to the desiccant gel handled through step 6 dropwise, be put into drying box and fully dry；Its
In, alkaline solution is NaOH solution, KOH solution or the ammoniacal liquor of mass concentration 35%~45%；
Step 8, by the desiccant gel handled through step 7 carry out carbonization treatment, using the tube furnace of both ends open, by 40cc
~60cc flows are passed through the nitrogen of air or purity not less than 99.999%, are warming up to according to 10 DEG C~50 DEG C speed per minute
650 DEG C~700 DEG C and be incubated 2~4 hours, Temperature fall, be made graphene/Spherical Carbon/metal oxide composite.
Embodiment 1
Weigh by mass percentage：Resorcinol solution 8%, formalin 5%, distilled water 80%, graphene suspension
3%, CoCl2·6H2O 4%, the content summation of above component is 100%；Wherein, the mass concentration of resorcinol solution is
10%；The mass concentration of formalin is 10%；Graphene-containing 10mg in every liter of graphene suspension；The resorcinol that will be weighed
Solution, formalin, graphene suspension and CoCl2·6H2O is added in the distilled water weighed, magnetic agitation 2h, is made anti-
Answer initial liquid；The obtained initial liquid of reaction is moved into the vial with seal closure, bottle cap is covered and is placed in drying box and coagulated
Glue reaction treatment, gel reaction temperature are 80 DEG C, and the gel reaction time is 30min, and wet gel is made；Obtained wet gel is put
It is placed in 80 DEG C of drying box and dries 1 hour, obtains desiccant gel；Configuration quality concentration is 25% salting liquid, wherein, salt is molten
Liquid is CoCl2·6H2O, salting liquid is instilled into desiccant gel dropwise, dripping quantity is 4 times of desiccant gel volumes, is then placed in drying
Case is fully dried, repeatedly, untill gel saturation；The NaOH solution of mass concentration 35% is instilled into the dry of processing dropwise
Dry gel, it is put into drying box and fully dries；The desiccant gel of processing is subjected to carbonization treatment, using the tube furnace of both ends open,
The nitrogen of air or purity not less than 99.999% is passed through by 40cc flows, 650 DEG C are warming up to according to 10 DEG C of speed per minute
And 2 hours are incubated, Temperature fall, graphene/Spherical Carbon/metal oxide composite is made.
Embodiment 2
Weigh by mass percentage：Resorcinol solution 20%, furfuryl aldehyde solution 5%, distilled water 65%, graphene suspension
5%, NiCl2·2H2O 5%, the content summation of above component is 100%；Wherein, the mass concentration of resorcinol solution is
20%；The mass concentration of furfuryl aldehyde solution is 20%；Graphene-containing 11mg in every liter of graphene suspension；The resorcinol that will be weighed
Solution, furfuryl aldehyde solution, graphene suspension and NiCl2·2H2O is added in the distilled water weighed, magnetic agitation 2.5h, is made
React initial liquid；The initial liquid of obtained reaction is moved into the vial with seal closure, bottle cap is covered and is placed in drying box and carry out
Gel reaction processing, gel reaction temperature are 85 DEG C, and the gel reaction time is 40min, and wet gel is made；By obtained wet gel
It is positioned in 85 DEG C of drying box and dries 1.5 hours, obtains desiccant gel；Configuration quality concentration is 30% salting liquid, wherein,
Salting liquid is NiCl2·2H2O solution, salting liquid is instilled into desiccant gel dropwise, dripping quantity is 4.5 times of desiccant gel volumes, so
After be put into drying box fully dry, repeatedly, untill gel saturation；The KOH solution of mass concentration 40% is dripped dropwise
Enter the desiccant gel of processing, be put into drying box and fully dry；The desiccant gel of processing is subjected to carbonization treatment, uses both ends open
Tube furnace, the nitrogen that air or purity is not less than 99.999% is passed through by 45cc flows, according to 20 DEG C of speed liters per minute
Temperature is to 660 DEG C and is incubated 3 hours, Temperature fall, graphene/Spherical Carbon/metal oxide composite is made.
Embodiment 3
Weigh by mass percentage：Quinol solution 10%, formalin 7%, distilled water 65%, graphene suspension
8%, CuCl2·2H2O 10%, the content summation of above component is 100%；Wherein, the mass concentration of quinol solution is
30%；The mass concentration of formalin is 30%；Graphene-containing 12mg in every liter of graphene suspension；The hydroquinones that will be weighed
Solution, formalin, graphene suspension and CuCl2·2H2O is added in the distilled water weighed, magnetic agitation 2.5h, is made
React initial liquid；The initial liquid of obtained reaction is moved into the vial with seal closure, bottle cap is covered and is placed in drying box and carry out
Gel reaction processing, gel reaction temperature are 90 DEG C, and the gel reaction time is 50min, and wet gel is made；By obtained wet gel
It is positioned in 90 DEG C of drying box and dries 2 hours, obtains desiccant gel；Configuration quality concentration is 30% salting liquid, wherein, salt
Solution is CuCl2·2H2O solution, salting liquid is instilled into desiccant gel dropwise, dripping quantity is 5 times of desiccant gel volumes, Ran Houfang
Enter drying box fully to dry, repeatedly, untill gel saturation；The ammoniacal liquor of mass concentration 40% is instilled into processing dropwise
Desiccant gel, it is put into drying box and fully dries；The desiccant gel of processing is subjected to carbonization treatment, uses the tubular type of both ends open
Stove, the nitrogen of air or purity not less than 99.999% is passed through by 50cc flows, 670 are warming up to according to 35 DEG C of speed per minute
DEG C and be incubated 3 hours, Temperature fall, be made graphene/Spherical Carbon/metal oxide composite.
Embodiment 4
Weigh by mass percentage：Quinol solution 12%, and furfuryl aldehyde solution 10%, distilled water 70%, graphene is suspended
Liquid 4%, ZnAc2H2O 4%, the content summation of above component is 100%；Wherein, the mass concentration of quinol solution is
50%；The mass concentration of furfuryl aldehyde solution is 50%；Graphene-containing 15mg in every liter of graphene suspension；The hydroquinones that will be weighed
Solution, furfuryl aldehyde solution, graphene suspension and ZnAc2H2O is added in the distilled water weighed, magnetic agitation 3h, is made anti-
Answer initial liquid；The obtained initial liquid of reaction is moved into the vial with seal closure, bottle cap is covered and is placed in drying box and coagulated
Glue reaction treatment, gel reaction temperature are 95 DEG C, and the gel reaction time is 60min, and wet gel is made；Obtained wet gel is put
It is placed in 100 DEG C of drying box and dries 3 hours, obtains desiccant gel；Configuration quality concentration is 35% salting liquid, wherein, salt
Solution is ZnAc2H2O solution, salting liquid is instilled into desiccant gel dropwise, dripping quantity is 5 times of desiccant gel volumes, Ran Houfang
Enter drying box fully to dry, repeatedly, untill gel saturation；By the NaOH solution of mass concentration 45% dropwise at instillation
The desiccant gel of reason, it is put into drying box and fully dries；The desiccant gel of processing is subjected to carbonization treatment, uses the pipe of both ends open
Formula stove, the nitrogen of air or purity not less than 99.999% is passed through by 60cc flows, is warming up to according to 50 DEG C of speed per minute
700 DEG C and be incubated 4 hours, Temperature fall, be made graphene/Spherical Carbon/metal oxide composite.
In step 1 of the present invention, resorcinol solution or quinol solution 8%~20%, formalin or furfural are selected
Solution 5%~10%, it is due to inside phenolic system, using benzenediol as material of main part, formaldehyde is based on as bridge formation part, formaldehyde
Carbon phase in benzenediol on phenyl ring connects, formed with captain's chain structure；Distilled water 65%~80% is selected as the molten of sol-gel
Agent, the direction connected between phenolic aldehyde sphere and macroporous structure are determined, so distilled water is more, be connected with each other between ball with more abundant
Space.But if distilling dilutional hyponatremia, phenolic aldehyde sphere is caused to float again and mutual not glue company.Graphene suspension 3%~8%, it is
Because graphene is as structural framing, because area is relatively large, very thin thickness, very light weight, density are minimum, so quality accounts for
Compare very little.Hydrosol-gel is prepared and can carried out under weak acid, mild alkaline conditions, and range of catalysts is extensive.
In step 3 of the present invention, from the vial with seal closure, it can effectively shorten gel time.
In step 4 of the present invention, tube furnace and inert gas shielding using both ends open, are in order to ensure heat treated
Carbon in journey in organic matter is not oxidized, also, tube furnace both ends open, is easy to air-flow to pass in and out；
In step 5 of the present invention, desiccant gel is instilled dropwise with salting liquid, is the metal ions M in order that sufficient amount+Fill
Divide, be uniformly dispersed or adsorb in spherical phenolic aldehyde and graphenic surface, so as to ensure that follow-up carbonization forms stable metal oxygen
Compound layer.
In step 7 of the present invention, desiccant gel is instilled dropwise with alkaline solution, is to introduce enough OH-Ion so that
Metal ions M in step 5+Metal base MOH is converted into, so that producing metal oxide during carbonization.
As shown in figure 1, through graphene/Spherical Carbon/metal oxide composite produced by the present invention, diameter about 2m's
Spherical Carbon adsorption the metal oxide layer that a layer thickness is about 10nm, and metal oxide particle is evenly distributed, thickness
Degree is uniform, without agglomeration.
As shown in Fig. 2 through graphene/Spherical Carbon/metal oxide composite produced by the present invention, ribbon graphene
The layer state that is interweaved in a three-dimensional structure, it is spaced apart by Spherical Carbon and metal oxide without occurring between graphene layer
Again stack.
Fig. 3 is that preparation method of the present invention and graphene/Spherical Carbon/metal oxide prepared by common preparation method are multiple
The cyclic voltammetry curve figure of condensation material, wherein, metal oxide is that ZnO sweep speeds are 20mV/s.As seen from Figure 3, originally
The closed area of invention preparation method curve is bigger than the closed area of common preparation method curve, illustrates the electrode specific volume of homogenous quantities
Amount compares, and preparation method of the present invention is bigger than the electrode specific capacity of common preparation method, also, the test electricity of preparation method of the present invention
It is 5mA or so to flow amplitude maximum, and the test current amplitude maximum of common preparation method is 0.78mA, is prepared through the present invention
Graphene/Spherical Carbon/metal oxide composite is more much larger than material current amplitude prepared by commonsense method, illustrates have more
Add excellent electric property.
Claims (5)
1. a kind of preparation method of graphene/Spherical Carbon/metal oxide composite, it is characterised in that specifically according to following
Step is implemented：
Step 1, weigh by mass percentage：Resorcinol solution or quinol solution 8%~20%, formalin or furfural
Solution 5%~10%, distilled water 65%~80%, graphene suspension 3%~8%, catalyst 4%~10%, above component
Content summation be 100%；
Step 2, by the resorcinol solution weighed through step 1 or quinol solution, formalin or furfuryl aldehyde solution, graphene
Suspension and catalyst are added in the distilled water weighed through step 1, stir, and the initial liquid of reaction is made；
It step 3, will be moved into through the obtained initial liquid of reaction of step 2 in the vial with seal closure, cover bottle cap and be placed in drying box
Middle progress gel reaction processing, is made wet gel；
Step 4, processing will be dried through wet gel made from step 3, and obtain desiccant gel；
Step 5, the salting liquid that configuration quality concentration is 25%~35%, desiccant gel, dripping quantity 4 are instilled by salting liquid dropwise
~5 times of desiccant gel volumes, it is then placed in drying box and fully dries；The salting liquid is CoCl2·6H2O、NiCl2·2H2O、
CuCl2·2H2O or ZnAc2H2O solution；
Step 6, repeat step more than 5 times, untill gel saturation；
Step 7, alkaline solution is instilled to the desiccant gel handled through step 6 dropwise, be put into drying box and fully dry；The alkalescence
Solution is NaOH solution, KOH solution or the ammoniacal liquor of mass concentration 35%~45%；
Step 8, the desiccant gel handled through step 7 is carried out to carbonization treatment, obtained graphene/Spherical Carbon/metal oxide is multiple
Condensation material, the specific implementation method of carbonization treatment are：Using the tube furnace of both ends open, air is passed through by 40cc~60cc flows
Or purity is not less than 99.999% nitrogen, is warming up to 650 DEG C~700 DEG C according to 10 DEG C~50 DEG C speed per minute and is incubated
2~4 hours, Temperature fall.
2. the preparation method of graphene/Spherical Carbon/metal oxide composite according to claim 1, its feature exist
In in the step 1, the mass concentration of resorcinol solution or quinol solution are 10%~50%；Formalin or chaff
The mass concentration of aldehyde solution is 10%~50%；Graphene-containing 10mg~15mg in every liter of graphene suspension；Catalyst is
CoCl2·6H2O、NiCl2·2H2O、CuCl2·2H2O or ZnAc2H2O。
3. the preparation method of graphene/Spherical Carbon/metal oxide composite according to claim 1, its feature exist
In in the step 2, stirring means are magnetic agitation, 2~3h of mixing time.
4. the preparation method of graphene/Spherical Carbon/metal oxide composite according to claim 1, its feature exist
In in the step 3, gel reaction temperature is 80 DEG C~95 DEG C, and the gel reaction time is 30min~60min.
5. the preparation method of graphene/Spherical Carbon/metal oxide composite according to claim 1, its feature exist
In in the step 4, the specific implementation method of drying process is：Obtained wet gel is positioned over to 80 DEG C~100 DEG C of drying
Dried 1~3 hour in case.
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| CN102515150A (en) * | 2011-12-08 | 2012-06-27 | 同济大学 | Method for preparing multilayer graphene-carbon material |
| CN102774824A (en) * | 2012-06-11 | 2012-11-14 | 北京化工大学 | Method for preparing graphene crosslinked type organic aerogel and carbon aerogel by normal-pressure drying |
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| US8993113B2 (en) * | 2010-08-06 | 2015-03-31 | Lawrence Livermore National Security, Llc | Graphene aerogels |
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| CN102515150A (en) * | 2011-12-08 | 2012-06-27 | 同济大学 | Method for preparing multilayer graphene-carbon material |
| CN102774824A (en) * | 2012-06-11 | 2012-11-14 | 北京化工大学 | Method for preparing graphene crosslinked type organic aerogel and carbon aerogel by normal-pressure drying |
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