CN105655154B - A kind of preparation method of graphene-activity Carbon composites electrode material for super capacitor - Google Patents
A kind of preparation method of graphene-activity Carbon composites electrode material for super capacitor Download PDFInfo
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- CN105655154B CN105655154B CN201610013075.2A CN201610013075A CN105655154B CN 105655154 B CN105655154 B CN 105655154B CN 201610013075 A CN201610013075 A CN 201610013075A CN 105655154 B CN105655154 B CN 105655154B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a kind of preparation method of graphene activity Carbon composites electrode material for super capacitor, raw material is mainly used as using egg white and graphene oxide, prepared with relatively low cost has the electrode material for super capacitor compared with Fabrication of High Specific Capacitance, multiplying power and cycle life at the same time, and concrete technical scheme main points are：By egg white magnetic agitation into foam-like thick slurry, while graphene oxide dispersion is added into egg white foams, form uniform compound slurry.Then the compound is placed in tube furnace and is successively carbonized and activation process in different temperatures, formation is provided simultaneously with micropore, mesoporous and macropore stratiform carbonaceous compound.Carbonaceous composite material prepared by the present invention can provide higher electric double layer and fake capacitance, be provided simultaneously with higher electronics and ionic conductivity, and superior fracture toughness, so as to specific volume, multiplying power and the cycle life of comprehensive raising capacitor.
Description
Technical field
The invention belongs to the preparing technical field of electrode material for super capacitor, and in particular to a kind of with electric double layer and counterfeit
The preparation method of the graphene of capacitance double grading-activity Carbon composites electrode material for super capacitor.
Background technology
Ultracapacitor is a kind of green, efficient and the long-life electrochemical energy storage device, has power density height, charge and discharge
The advantages that operating temperature range electric quick, service life is long, wider and safety non-pollution, in smart electronics product, electronic
There is important use in the fields such as instrument, hybrid vehicle and highpowerpulse equipment.
Specific surface area, good corrosion resistance, relatively low manufacturing cost and abundant raw material of the activated carbon with superelevation etc. are special
Point, therefore be most commonly used electric double layer electrode material in ultracapacitor.But activated carbon electric conductivity is relatively poor, its is micro-
Pore structure can not only limit its surface utilisation, nor beneficial to the quick scattering and permeating of electrolyte ion, cause relatively low
Specific volume and high rate performance.The heterogeneous element of fake capacitance activity is introduced in porous active carbon surface, then can be contributed by fake capacitance big
Width improves the specific volume of ultracapacitor.At the same time by optimizing pore passage structure and the aperture of activated carbon, improve times of ultracapacitor
Rate performance, so that suitable for fast charging and discharging under conditions of high current.Therefore, the composition to porous carbon materials and structure,
It is the key link for lifting ultracapacitor energy storage performance that surface characteristic, which rationally design,.
Graphene is a kind of new ultra-thin carbon material, has excellent electric conductivity, mechanical strength and larger ratio surface
Product, there is important application prospect in terms of electrode material for super capacitor.But the higher surface energy of graphene causes it easily
Reunite, thus it is relatively low to be directly used in electrode material capacitance.Graphene is incorporated among activated carbon, forms carbonaceous composite material,
Not only graphene sheet layer reunion can have been limited, but also being conductively connected between active carbon particle and fracture toughness can be improved, so as to carry
The multiplying power and cycle life of high capacitance.Using suitable raw material, prepared by rational strategy with high-specific surface area, reasonable hole
The electrode material of the electric double layer of footpath and pore structure, fake capacitance double grading, be comprehensive raising ultracapacitor specific volume, multiplying power and
The key of cycle life.
For graphene-absorbent charcoal composite material, due to activated carbon for solid phase and also pattern it is irregular, directly pass through
Graphene and for composite prepare of activated carbon are difficult to the pattern and pore structure of Effective Regulation composite material, choose liquid phase presoma into
Row prepare then can Effective Regulation compound pattern, and make to come into full contact between graphene and activated carbon, establish efficent electronic, electricity
Solve matter transmission channels and fracture toughness, specific volume, multiplying power and the cycle life of comprehensive raising ultracapacitor.
The content of the invention
The technical problem to be solved by the present invention is to provide a kind of multistage pore canal sheet cross-linked structure graphene-activated carbon is multiple
The preparation method of compound electrode material for super capacitor, specific volume, multiplying power and the circulation of the comprehensive raising ultracapacitor of this method
Specific volume under performance, particularly higher current density.
The present invention adopts the following technical scheme that a kind of graphene-activity Carbon composites are super to solve above-mentioned technical problem
The preparation method of capacitor electrode material, it is characterised in that concretely comprise the following steps：10mL fresh albumens are poured into container and are stirred
30min forms sticky egg white foams, 0.01g graphene oxides is added in 100mL deionized waters, ultrasonic disperse 30min, then
Centrifuged with the speed of 12000 turns/min, discard insoluble precipitation, supernatant rotary evaporation is concentrated into the thick slurry of 15mL, by this
Thick slurry is added in egg white foams, and stirring 120min forms light brown mixture foam, then the mixture foam is dry in 60 DEG C
It is transferred to after dry in tube furnace, is heated to 500 ~ 800 DEG C of calcining 0.5 ~ 4h of carbonization under an inert atmosphere, graphite is obtained after cooling
Alkene-activated carbon precursor, then mixes graphene-activated carbon precursor with potassium hydroxide, and is transferred in nickel crucible lazy
Property atmosphere under washed after 500 ~ 800 DEG C of 0.5 ~ 4h of calcining and activating, cooling with hydrochloric acid and deionized water to neutrality, then it is filtered and
It is dried to obtain graphene-activity Carbon composites electrode material for super capacitor.
Further limit, the mass ratio of the graphene-activated carbon precursor and potassium hydroxide is 1:3, inert atmosphere
For helium, nitrogen or argon gas.
The peptide chain of the albumen of the present invention has different hydrophobic and hydrophilic regions, can be used as amphipathic surface-active
Agent；Graphene oxide is made of the flexible hydrophobic aromatic carbocyclic ring of hydrophilic radical functionalization, is equally considered as surface-active
Material；Both fluid behaviours enable to form uniform compound by polarity and hydrophobic effect, while contain in both
Oxygen and nitrogen heterogeneous element can be used as to provide fake capacitance, thus by carbonization and activation process can comprehensive raising it is super
Specific volume, multiplying power and the cycle performance of capacitor.With existing graphene compared with being simply mixed of activated carbon, prepared in the present invention
Graphene and activated carbon are conductively connected more fully in product, its cross-linked structure and the distribution of wider bore footpath be more advantageous to electronics and electricity
The diffusion transport of matter ion is solved, the high rate performance of higher can be obtained.
Brief description of the drawings
Fig. 1 is the transmission electricity of graphene made from the embodiment of the present invention 2-activity Carbon composites electrode material for super capacitor
Mirror figure, as seen from the figure activated carbon form uniform deposition layer in graphene surface, crosslinked multidimensional stratiform knot is integrally formed in compound
Structure, there is wider interlayer hole, is conducive to being sufficient filling with diffusion transport and being come into full contact with electrode surface for electrolyte, has
Beneficial to acquisition higher specific volume and high rate performance；
Fig. 2 is the forthright again of graphene made from the embodiment of the present invention 2-activity Carbon composites electrode material for super capacitor
Can curve；
Fig. 3 is the scanning electricity of graphene made from the embodiment of the present invention 2-activity Carbon composites electrode material for super capacitor
Mirror figure.
Embodiment
The above of the present invention is described in further details with reference to embodiment.The present embodiment is with skill of the present invention
It is lower premised on art scheme to implement, give detailed embodiment and operating process, but protection scope of the present invention be not limited to
Lower embodiment.
Embodiment 1
By 10mL fresh albumens（Egg white volume in about half piece of egg）Pour into beaker stir 30min formed it is sticky
Egg white foams；0.01g graphene oxides are added in 100mL deionized waters, ultrasonic disperse 30min, with the speed of 12000 turns/min
Rate centrifuges, and discards insoluble precipitation, and supernatant rotary evaporation is concentrated into the thick slurry of 15mL, which is added
Egg white foams, stirring 120min form light brown mixture foam.By the mixture foam after 60 DEG C dry, tubular type is transferred to
In stove, 650 DEG C of calcining carbonization 2h are heated under nitrogen protection, graphene-activated carbon precursor are obtained after cooling, by graphite
Alkene-activated carbon precursor is with potassium hydroxide with mass ratio 1:3 mixing, are transferred in nickel crucible, are forged under nitrogen protection in 650 DEG C
Activation 2h is burnt, is washed after cooling with hydrochloric acid and deionized water to neutrality, then it is multiple by filtering and being dried to obtain graphene-activated carbon
Compound electrode material for super capacitor.
By the graphene prepared by 4.25g-activity Carbon composites electrode material for super capacitor, according to electrode material：Second
Acetylene black：Polytetrafluoroethylene (PTFE)=85:10:5 mass ratio mixing, grinding are formed uniformly slurry, are coated on stainless steel collector, are made
Electrode of super capacitor, is assembled into symmetrical ultracapacitor.Constant current charge-discharge test shows that made ultracapacitor exists
Quality specific volume reaches 267F/g under 1A/g current densities.
Embodiment 2
By 10mL fresh albumens（Egg white volume in about half piece of egg）Pour into beaker stir 30min formed it is sticky
Egg white foams；0.1g graphene oxides are added in 100mL deionized waters, ultrasonic disperse 30min, with the speed of 12000 turns/min
Rate centrifuges, and discards and does not allow to precipitate, and supernatant rotary evaporation is concentrated into the thick slurry of 15mL, which is added
Egg white foams, stirring 120min form light brown mixture foam.By the mixture foam after 60 DEG C dry, tubular type is transferred to
In stove, 650 DEG C of calcining carbonization 2h are heated under nitrogen protection, graphene-activated carbon precursor are obtained after cooling, by graphite
Alkene-activated carbon precursor is with potassium hydroxide with mass ratio 1:3 mixing, are transferred in nickel crucible, are forged under nitrogen protection in 650 DEG C
Activation 2h is burnt, is washed after cooling with hydrochloric acid and deionized water to neutrality, then it is multiple by filtering and being dried to obtain graphene-activated carbon
Compound electrode material for super capacitor（Fig. 1）.
Obtained graphene-activity Carbon composites electrode material for super capacitor is made according to the method for embodiment 1 and is surpassed
Level capacitor.As shown in Fig. 2, ultracapacitor quality specific volume under 1A/g current densities reaches 291F/g, in 15A/g electric currents
Quality specific volume reaches 229F/g under density；In 0.5 ~ 15A/g current density ranges, specific volume conservation rate reaches 69%, shows excellent
High rate performance more.Specific volume remains to holding 90% after 5000 discharge and recharges at the same time, has good cycle life.
Embodiment 3
By 10mL fresh albumens（Egg white volume in about half piece of egg）Pour into beaker stir 30min formed it is sticky
Egg white foams；0.1g graphene oxides are added in 100mL deionized waters, ultrasonic disperse 30min, with 12000 turns/min's
Speed centrifuges, and discards and does not allow to precipitate, supernatant rotary evaporation is concentrated into the thick slurry of 15 mL, by the graphene oxide thick slurry
Egg white foams are added, stirring 120min forms light brown mixture foam.By the mixture foam after 60 DEG C dry, it is transferred to
In tube furnace, 800 DEG C of calcining carbonization 2h are heated under nitrogen protection, graphene-activated carbon precursor are obtained after cooling, by stone
Black alkene-activated carbon precursor is with potassium hydroxide with mass ratio 1:3 mixing, are transferred in nickel crucible, under nitrogen protection in 800 DEG C
Calcining and activating 2h, is washed to neutrality after cooling with hydrochloric acid and deionized water, then by filtering and is dried to obtain graphene-activated carbon
Compound electrode material for super capacitor.
Obtained graphene-activity Carbon composites electrode material for super capacitor is made according to the method for embodiment 1 and is surpassed
Level capacitor.Ultracapacitor quality specific volume under 1A/g current densities is reduced to 213F/g.
, can be significantly by embodiment as can be seen that by adjusting egg white and graphene oxide ratio and carbonization, activation temperature
Optimize the capacitive property of graphene activated carbon composite materials.
It is above the exemplary embodiments of the present invention, these embodiments main feature that the invention has been described and particular implementation bar
Capacitive property under part, not limiting the scope of the present invention, all experiment conditions according to the design thinking change and change
Into within the scope of the present invention.
Claims (2)
- A kind of 1. preparation method of graphene-activity Carbon composites electrode material for super capacitor, it is characterised in that specific steps For：10mL fresh albumens are poured into stirring 30min in container and form sticky egg white foams, 0.01g graphene oxides are added In 100mL deionized waters, ultrasonic disperse 30min, then centrifuged with the speed of 12000 turns/min, discard insoluble precipitation, supernatant Liquid rotary evaporation is concentrated into the thick slurry of 15mL, which is added in egg white foams, and stirring 120min forms light brown mixing Thing foam, then the mixture foam is transferred in tube furnace after 60 DEG C of dryings, 500 ~ 800 DEG C are heated under an inert atmosphere Calcining 0.5 ~ 4h of carbonization, obtains graphene-activated carbon precursor, then by graphene-activated carbon precursor and hydrogen-oxygen after cooling Change potassium mixing, and be transferred in nickel crucible under an inert atmosphere in 500 ~ 800 DEG C of 0.5 ~ 4h of calcining and activating, after cooling with hydrochloric acid and Deionized water is washed to neutrality, then filtered and be dried to obtain graphene-activity Carbon composites electrode material for super capacitor.
- 2. the preparation method of graphene according to claim 1-activity Carbon composites electrode material for super capacitor, it is special Sign is：Graphene-the activated carbon precursor and the mass ratio of potassium hydroxide are 1:3, inert atmosphere for helium, nitrogen or Argon gas.
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| CN106450397B (en) * | 2016-09-20 | 2019-06-04 | 福建农林大学 | A kind of preparation method of nitrogen-doped graphene electrode material |
| CN108435134B (en) * | 2018-05-10 | 2019-10-18 | 中南大学 | Egg white-graphene oxide self-assembled compound material preparation and its application |
| CN110467175B (en) * | 2019-09-19 | 2021-01-08 | 深圳烯创先进材料研究院有限公司 | Preparation method of graphene-reinforced biomass porous carbon electromagnetic wave-absorbing material |
| CN111029168B (en) * | 2019-12-24 | 2021-09-17 | 东北电力大学 | Egg white derived biomass charcoal-loaded silver nanoparticle electrode material and preparation method thereof |
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| CN103730638A (en) * | 2013-10-12 | 2014-04-16 | 吉林大学 | Preparation method of nitrogen-doped carbon material |
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| CN103730638A (en) * | 2013-10-12 | 2014-04-16 | 吉林大学 | Preparation method of nitrogen-doped carbon material |
| CN103824701A (en) * | 2014-03-11 | 2014-05-28 | 中国第一汽车股份有限公司 | Active graphene composite electrode material |
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