CN106082210A - A kind of compound active fruit shell carbon and preparation method thereof, application - Google Patents
A kind of compound active fruit shell carbon and preparation method thereof, application Download PDFInfo
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- CN106082210A CN106082210A CN201610445281.0A CN201610445281A CN106082210A CN 106082210 A CN106082210 A CN 106082210A CN 201610445281 A CN201610445281 A CN 201610445281A CN 106082210 A CN106082210 A CN 106082210A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides the preparation method of a kind of compound active fruit shell carbon, comprise the following steps, first the active fruit shell carbon powder after steam activation is mixed with alkali, after overactivation, obtain semi-finished product；Then after again being mixed with graphene oxide solution by the semi-finished product that above-mentioned steps obtains, carry out reduction reaction, obtain compound active fruit shell carbon.The compound active fruit shell carbon of the offer of the present invention, activation shell class activated carbon is combined by physics and chemical method, pulverized by the shell class activated carbon that steam activation is crossed, carry out alkali activation again, then combined oxidation Graphene, high temperature reduction, obtain the compound active fruit shell carbon that Graphene is modified, effectively overcome the shortcomings such as shell class activated carbon electrical conductivity is low, specific surface area is little, can use directly as the activated carbon of ultracapacitor, greatly improve the value of shell class activated carbon and expand the application of active fruit shell carbon.
Description
Technical field
The invention belongs to absorbent charcoal material technical field, particularly relate to a kind of compound active fruit shell carbon and preparation side thereof
Method, application.
Background technology
Activated carbon, also known as activated carbon black, is black powder or bulk, graininess, cellular amorphous carbon, also has row
Arrange regular crystal carbon.In activated carbon outside de-carbon element, also comprise a small amount of protium and oxygen element, a part of source of these elements
Remain in activated carbon in the incomplete carbonization of activated carbon precursor, another part derive from activating reagent such as water or sodium hydroxide with
Activated carbon surface reaction forms the groups such as hydroxyl, carboxyl, carbonyl.In addition activated carbon there is also a part of ash, mainly by remaining
Inorganic salt composition in activated carbon, such as iron salt, sodium salt, potassium salt etc..
Activated carbon divide from raw material can be divided into wooden, ature of coal, petroleum coke and resin activity charcoal；Come from manufacture method
Point, it is divided into chemical method, Physical and physical chemistry combination method activated carbon.These activated carbon precursors in activation furnace in high temperature,
Activated carbon is formed with activator by pyrolysis, high temperature carbonization and priming reaction under certain pressure.In this activation process, huge
Big surface area and complicated pore structure gradually form.Activated carbon contains a large amount of micropore, has huge incomparable surface area, energy
Effectively removing colourity, stink, in removable secondary effluent, most organic pollutants and some inorganic matter, comprise some poisonous
Heavy metal.And according to activated carbon graphitization complexity, it is divided into again hard carbon and soft carbon, with lignin, resin it is as a rule
Raw material prepare for hard charcoal, with petroleum coke for raw material prepare as soft charcoal.
In activated carbon prepared by numerous materials, active fruit shell carbon is the most concerned a kind of activated carbon, this
Black particle shape active fruit shell carbon, selecting the shells such as high-quality environmental protection coconut husk, peach shell, walnut shell, Fructus Pruni shell is raw material, employing carbonization,
The techniques such as activation, superheated steam catalysis are refined to be formed, and outward appearance is black indefinite form granule, through produced in series processes
A kind of activated carbon.Owing to the raw material of active fruit shell carbon and coal mass active carbon is different, usual active fruit shell carbon is than ature of coal activity
Charcoal is light, and coal mass active carbon cannot be used for drinking water treatment, and active fruit shell carbon is just widely used in drink owing to raw material is natural
In processing with water, and shell class activated carbon does not have poisonous and harmful substance dissolution in the fine filtering carrying out water quality.And
Active fruit shell carbon also has the advantages such as wear-resisting intensity is good, space is flourishing, absorption property is high, intensity is high, easy regeneration, economy and durability,
It is widely used in life, industry, liquid phase adsorption, purification of water quality, Gas Phase Adsorption, is particularly well-suited to power plant, petrochemical industry, oil plant, print
The industries such as dye textile industry, food and drink, medicinal water, electronics high purity water, Drinking Water, Reuse of Industrial Reclaimed Water, more can be effective
Free chlorine, phenol, sulfur, oil, colloid, pesticide residue and other organic pollutions in absorption water, chlorine residue, half de-chlorine value, and
The recovery etc. of organic solvent.However as science and technology fast development, the every profession and trade performance further requirement to active fruit shell carbon, as
What is broken through the limitation of reality application, adapts to the demand of many industries application, it has also become a kind of direction of research.
Therefore, how to obtain the active fruit shell carbon of a kind of modification, expand the application of active fruit shell carbon, to shell activity
The actual application of charcoal is significant, and also becomes one of focus of perspective study personnel's extensive concern in field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention be to provide the compound active fruit shell carbon of a kind of modification and
Preparation method, application, the Graphene that the present invention provides is combined active fruit shell carbon, it is possible to the specific surface of the effective activated carbon improved
Long-pending, it is possible to as Supercapacitor carbon, to obtain the ultracapacitor with relatively high specific capacitance.
The invention provides the preparation method of a kind of compound active fruit shell carbon, comprise the following steps:
A) the active fruit shell carbon powder after steam activation is mixed with alkali, then after overactivation, obtain activated carbon semi-finished product；
B) after activated carbon semi-finished product above-mentioned steps obtained mix again with graphene oxide solution, and it is anti-to carry out reduction
Should, obtain compound active fruit shell carbon.
Preferably, one or more during described alkali includes potassium hydroxide, sodium hydroxide and calcium hydroxide；
Described active fruit shell carbon powder is 1:(0.5～2 with the mass ratio of alkali).
Preferably, the temperature of described activation is 600～950 DEG C, and the time of described activation is 0.5～4h.
Preferably, the granularity of described active fruit shell carbon powder is 8～12 μm；The average sheet footpath of described graphene oxide be 1～
50μm；
It is 0.1%～1% that the quality of described graphene oxide accounts for the ratio of described active fruit shell carbon opaque amount.
Preferably, described reduction reaction is particularly as follows: carry out reduction reaction under conditions of protective gas；
Described protective gas includes one or more in hydrogen, ammonia and nitrogen；
The temperature of described reduction reaction is 650～1200 DEG C, and the time of described reduction reaction is 1～6h.
Preferably, described step B) particularly as follows:
B`) after activated carbon semi-finished product, nitrogen source and graphene oxide solution above-mentioned steps obtained mixes again, and carry out
Reduction reaction, obtains compound active fruit shell carbon.
Preferably, described nitrogen source includes tripolycyanamide and/or carbamide；
It is 1%～3% that the quality in described nitrogen source accounts for the ratio of described active fruit shell carbon opaque amount.
The present invention provides a kind of compound active fruit shell carbon, including active fruit shell carbon and the Graphene being compounded in its surface
Layer.
Preferably, described compound active fruit shell carbon is obtained after compound by active fruit shell carbon, graphene oxide and nitrogen source
Arrive.
The invention provides a kind of ultracapacitor, comprise the compound shell prepared by technique scheme any one
Compound active fruit shell carbon described in activated carbon or technique scheme any one.
The invention provides the preparation method of a kind of compound active fruit shell carbon, comprise the following steps, first by steam
Active fruit shell carbon powder after activation mixes with alkali, then obtains activated carbon semi-finished product after overactivation；Then above-mentioned steps is obtained
Semi-finished product again mix with graphene oxide solution after, and carry out reduction reaction, obtain compound active fruit shell carbon.With existing
Technology is compared, the compound active fruit shell carbon of the offer of the present invention, combines activation shell class activated carbon by physics and chemical method,
Being pulverized by the shell class activated carbon crossed by steam activation, then carry out alkali activation, then combined oxidation Graphene, high temperature is also
Former, obtain the compound active fruit shell carbon that Graphene is modified, effectively overcome that shell class activated carbon electrical conductivity is low, specific surface
Amass the shortcomings such as little, it is possible to the activated carbon directly as ultracapacitor uses, and greatly improves shell class activated carbon
It is worth and expands the application of active fruit shell carbon.Test result indicate that, the specific surface of shell class activated carbon prepared by the present invention
Amass 1600～2400m2Between/g, after being prepared as finished product ultracapacitor, the quality of material can reach 160F/g than electric capacity.
Accompanying drawing explanation
The Electronic Speculum figure of the compound active fruit shell carbon that Fig. 1 provides for the present invention；
Fig. 2 is the Electronic Speculum figure of the compound active fruit shell carbon of the embodiment of the present invention 1 preparation；
Fig. 3 is the performance detection figure of the ultracapacitor of the embodiment of the present invention 1 preparation.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but
Should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention rather than to invention claim
Limit.
The all raw materials of the present invention, are not particularly limited its source, that commercially buy or according to people in the art
Prepared by the conventional method known to Yuan.
The all raw materials of the present invention, are not particularly limited its purity, present invention preferably employs analytical pure or capacitor area
The conventional purity used.
The invention provides the preparation method of a kind of compound active fruit shell carbon, comprise the following steps:
A) the active fruit shell carbon powder after steam activation is mixed with alkali, then after overactivation, obtain activated carbon semi-finished product；
B) after activated carbon semi-finished product above-mentioned steps obtained mix again with graphene oxide solution, and it is anti-to carry out reduction
Should, obtain compound active fruit shell carbon.
Described shell is not particularly limited by the present invention, with well known to those skilled in the art for preparing active fruit shell carbon
Shell, shell of the present invention is preferably the shells such as coconut husk, peach shell, walnut shell, Fructus Pruni shell, more preferably coconut husk and/or
Fructus Pruni shell.The source of described active fruit shell carbon powder is not particularly limited by the present invention, with shell carbon well known to those skilled in the art
Active fruit shell carbon after change, those skilled in the art can be carried out according to practical condition, product requirement and prescription
Selecting and adjust, the shell class activated carbon that the present invention crosses through steam activation preferably past carbonization again obtains after crushed.
The granularity of described active fruit shell carbon powder is not particularly limited by the present invention, with active fruit shell carbon powder well known to those skilled in the art
Granularity, those skilled in the art can select according to practical condition, product requirement and prescription and adjust
Whole, the granularity of active fruit shell carbon powder of the present invention is preferably 8～12 μm, more preferably 8.5～11.5 μm, more preferably 9～
11 μm, most preferably 9.5～10.5 μm.
Described alkali is not particularly limited by the present invention, with the alkali of alkali well known to those skilled in the art activation active fruit shell carbon
, those skilled in the art can select according to practical condition, product requirement and prescription and adjust, this
Bright described alkali preferably includes one or more in potassium hydroxide, sodium hydroxide and calcium hydroxide, more preferably potassium hydroxide, hydrogen
Sodium oxide or calcium hydroxide, most preferably potassium hydroxide.Described alkali can be added or molten with alkali by the present invention in solid form
The form of liquid adds, those skilled in the art can carry out selecting according to practical condition, product requirement and prescription and
Adjusting, when adding fashionable with the form of aqueous slkali, the concentration of described aqueous slkali is not particularly limited by the present invention, with art technology
The alkaline concentration of the alkali activation active fruit shell carbon known to personnel, those skilled in the art can be according to actual production feelings
Condition, product requirement and prescription select and adjust.The addition of described aqueous slkali is not particularly limited by the present invention, this
Skilled person can select according to practical condition, product requirement and prescription and adjust, of the present invention
Active fruit shell carbon powder is preferably 1:(0.5～2 with the mass ratio of alkali), more preferably 1:(0.75～1.75), more preferably 1:(1
～1.5), most preferably 1:(1.1～1.4).
The condition of described activation is not particularly limited by the present invention, with activation condition well known to those skilled in the art i.e.
Can, those skilled in the art can select according to practical condition, product requirement and prescription and adjust, the present invention
The temperature of described activation is preferably 600～950 DEG C, more preferably 650～900 DEG C, more preferably 700～850 DEG C, most preferably
750～800 DEG C；The time of described activation is preferably 0.5～4h, more preferably 1～3.5h, more preferably 1.5～3h, most preferably
It is 2～2.5h；The heating rate of described activation is preferably 5～20 DEG C/min, more preferably 7.5～17.5 DEG C/min, more preferably
It is 10～15 DEG C/min, most preferably 11～14 DEG C/min；Described activation is preferably carried out under the protection of noble gas or nitrogen.
The equipment of described activation is not particularly limited by the present invention, with activation equipment well known to those skilled in the art, this area
Technical staff can select according to practical condition, product requirement and prescription and adjust, activation of the present invention
Equipment be preferably activation furnace.
After the activated carbon semi-finished product that above-mentioned steps is obtained by the present invention subsequently mix again with graphene oxide solution, go forward side by side
Row reduction reaction, obtains compound active fruit shell carbon.
Graphene oxide solution of the present invention is preferably single-layer graphene oxide solution, and described monolayer rate is preferably above
In 95%.The source of described single-layer graphene oxide solution is not particularly limited by the present invention, knows with those skilled in the art
The source of single-layer graphene oxide solution, commercially available buying can also be prepared according to conventional preparation method.This
The bright addition to described graphene oxide solution is not particularly limited, and those skilled in the art can be according to actual production feelings
Condition, product requirement and prescription select and adjust, and the quality of graphene oxide of the present invention accounts for described shell activity
The ratio of powdered carbon quality is preferably 0.1%～1%, more preferably 0.2%～0.9%, more preferably 0.2%～0.8%, optimum
Elect 0.3%～0.7% as.The sheet footpath of described graphene oxide is not particularly limited by the present invention, ripe with those skilled in the art
The sheet footpath of the graphene oxide known, those skilled in the art can want according to practical condition, product requirement and quality
Asking and select and adjust, the average sheet footpath of graphene oxide of the present invention is preferably 1～50 μm, more preferably 5～45 μm,
More preferably 10～40 μm, most preferably 20～30 μm.
The condition of described reduction reaction is not particularly limited by the present invention, and those skilled in the art can be according to actual production
Situation, product requirement and prescription select and adjust, and the temperature of reduction reaction of the present invention is preferably 650～1200
DEG C, more preferably 750～1100 DEG C, more preferably 850～1000 DEG C, most preferably 900～950 DEG C；Described reduction reaction
Time is preferably 1～6h, more preferably 2～5h, more preferably 2.5～4.5h, most preferably 3～4h；Described reduction reaction
Heating rate is preferably 5～20 DEG C/min, more preferably 7.5～17.5 DEG C/min, more preferably 10～15 DEG C/min, most preferably
It is 11～14 DEG C/min；Described reduction reaction is also particularly preferred as, and carries out reduction reaction under conditions of protective gas；Described
Protective gas preferably includes one or more in hydrogen, ammonia and nitrogen, more preferably hydrogen or nitrogen, most preferably nitrogen
Gas.The equipment of described reduction reaction is not particularly limited by the present invention, with reduction reaction equipment well known to those skilled in the art
, those skilled in the art can select according to practical condition, product requirement and prescription and adjust, this
The equipment of bright described reduction reaction is preferably reduction furnace.
The present invention is to improve the compound active fruit shell carbon characteristic as ultracapacitor charcoal further, promotes electrode material
Capacity, described step B) be particularly preferred as, activated carbon semi-finished product, nitrogen source and the graphene oxide solution that above-mentioned steps is obtained
Again after mixing, and carry out reduction reaction, obtain compound active fruit shell carbon.
Described nitrogen source is not particularly limited by the present invention, and those skilled in the art can be according to practical condition, product
Requiring and prescription selects and adjusts, nitrogen source of the present invention is preferably little molecule nitrogen-containing compound (nitrogenous little point
Son), more preferably tripolycyanamide and/or carbamide, more preferably tripolycyanamide or carbamide, most preferably tripolycyanamide.The present invention
The addition in described nitrogen source is not particularly limited, those skilled in the art can according to practical condition, product requirement and
Prescription selects and adjusts, and the quality in nitrogen source of the present invention accounts for the ratio of described active fruit shell carbon opaque amount and is preferably
1%～3%, more preferably 1.25%～2.75%, more preferably 1.5%～2.5%, most preferably 1.75%～2.25%.
The present invention has prepared compound active fruit shell carbon through above-mentioned steps, and the present invention is to the auxiliary in preparation process
Step is not particularly limited, and those skilled in the art can select according to practical condition, product requirement and prescription
Selecting and adjust, the shell class activated carbon powder after above-mentioned steps of the present invention is specifically as follows steam activation adds after alkali steeping,
Vacuum drying；The activation furnace heating added under nitrogen protection activates, and obtains activated carbon semi-finished product；
Then above-mentioned activated carbon semi-finished product are carried out being washed to neutrality, pickling, again wash, more water-soluble with graphene oxide
Liquid and containing nitrogen precursor mix, be combined by spray drying, finally carry out adding thermal reduction in reduction furnace, improve surface official's energy
Group's performance.
The present invention is to the concrete operations of the vacuum drying in above-mentioned steps, washing, pickling and spray drying and condition
It is not particularly limited, with routine operation and the condition of above-mentioned steps well known to those skilled in the art.
The compound active fruit shell carbon that above-mentioned steps of the present invention provides, is former by passing through physically activated fruit shell carbon
Material, is activated duct by aqueous slkali further, and having obtained having suitable specific surface area is 1600～2400m2/ g's
Fruit shell carbon, the alkali number not only used is less, and technique is simpler than directly preparing Supercapacitor carbon from shell；And pass through
In the fruit shell carbon of re-activation, add graphene oxide and be combined containing nitrogen precursor spray drying, it is possible to achieve graphene oxide
Uniformly cladding on fruit shell carbon surface and nitrogenous precursor are at the uniform fold of activated carbon surface；At high temperature reduction heat subsequently
During reason, graphene oxide is reduced to Graphene, so that activated carbon has higher electrical conductivity, reduces in material with carbon element
Resistance；Reacted at surface formation nitrogen-containing group containing nitrogen precursor and surface functional group by high temperature, improve activated carbon surface Nitrogen content, from
And improve the specific capacity of Supercapacitor carbon, use as the activated carbon of ultracapacitor and can greatly promote shell class activated carbon
It is worth and expands the application of active fruit shell carbon.
The invention provides a kind of compound active fruit shell carbon, including active fruit shell carbon and the Graphene being compounded in its surface
Layer.
Described being combined is not particularly limited by the present invention, with compound concept well known to those skilled in the art, and can
Think cladding, be partly coated with, spray, bond or embed in one or more.Compound active fruit shell carbon of the present invention is more excellent
Select and obtained after compound by active fruit shell carbon, graphene oxide and nitrogen source.
See the Electronic Speculum figure of the compound active fruit shell carbon that Fig. 1, Fig. 1 provide for the present invention.
Present invention also offers a kind of ultracapacitor, comprise the compound fruit prepared by technique scheme any one
Compound active fruit shell carbon described in shell activated carbon or technique scheme any one.The present invention is to described ultracapacitor
Definition is not particularly limited, with the definition of ultracapacitor well known to those skilled in the art.
Test result indicate that, the specific surface area of shell class activated carbon prepared by the present invention is 1600～2400m2Between/g,
After being prepared as finished product ultracapacitor, the quality of material can reach 160F/g than electric capacity.
In order to further illustrate the present invention, the compound active fruit shell carbon that the present invention provided below in conjunction with embodiment and
Preparation method, application are described in detail, but it is to be understood that these embodiments are under premised on technical solution of the present invention
Implement, give detailed embodiment and concrete operating process, simply for further illustrate inventive feature with
Advantage rather than limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiment.
Embodiment 1
Take 100g fruit shell carbon and be crushed to 8～12 μm；50g potassium hydroxide is dissolved in 50mL water, mixes with fruit shell carbon
Close uniformly, be dried under vacuum；Then above-mentioned material is added in the activation furnace of nitrogen protection, with the ramp of 5 DEG C/min extremely
780 DEG C and keep 2h；After being cooled to room temperature, activation products are washed to neutrality, are subsequently adding the hydrochloric acid reflux 2h of 6M, again use
Deionized water is washed till neutrality；Add the graphene oxide aqueous dispersions of 300mL0.6% concentration, and be added thereto to 2g melamine
Amine, ultrasonic agitation 1h, then it is spray-dried；Above-mentioned material is placed in reduction furnace, with the speed of 10 DEG C/min under hydrogen shield
Rate is warming up to 900 DEG C and keeps 2h；After temperature is down to room temperature, i.e. obtain the shell base Supercapacitor carbon that Graphene is modified.
See the Electronic Speculum figure of the compound active fruit shell carbon that Fig. 2, Fig. 2 are the embodiment of the present invention 1 preparation.
Detecting the modified shell base Supercapacitor carbon of above-described embodiment 1 preparation, specific surface area is 1650m2/g。
This activated carbon is mixed homogenate with binding agent SBR with CMC, is uniformly coated on aluminium foil, drying, roll, punching
After be assembled into ultracapacitor (organic system, 2.7V).
The ultracapacitor of above-described embodiment 1 preparation is carried out performance detection, and seeing Fig. 3, Fig. 3 is the embodiment of the present invention 1
The performance detection figure of the ultracapacitor of preparation.Be can be calculated by Fig. 3, when electric current density is 2A/g, quality is 135F/ than electric capacity
g。
Embodiment 2
Take 100g fruit shell carbon and be crushed to 8～12um；100g potassium hydroxide is dissolved in 100mL water, with fruit shell carbon
Mix homogeneously, is dried under vacuum；Then above-mentioned material is added in the activation furnace of nitrogen protection, with the ramp of 5 DEG C/min
To 780 DEG C and keep 2h；After being cooled to room temperature, activation products are washed to neutrality, are subsequently adding the hydrochloric acid reflux 2h of 6M, again
It is washed with deionized water to neutrality；Add the graphene oxide aqueous dispersions of 300mL0.6% concentration, and be added thereto to 2g trimerization
Cyanamide, ultrasonic agitation 1h, then it is spray-dried；Above-mentioned material is placed in reduction furnace, with 10 DEG C/min's under hydrogen shield
Ramp is to 900 DEG C and keeps 2h；Temperature i.e. obtains the shell base Supercapacitor carbon that Graphene is modified after being down to room temperature.
Detecting the modified shell base Supercapacitor carbon of above-described embodiment 2 preparation, specific surface area is 2050m2/g。
This activated carbon is mixed homogenate with binding agent SBR with CMC, is uniformly coated on aluminium foil, drying, roll, punching
After be assembled into ultracapacitor (organic system, 2.7V).
The ultracapacitor of above-described embodiment 2 preparation is carried out performance detection, when electric current density is 2A/g, mass ratio electricity
Hold for 140F/g.
Embodiment 3
Take 100g fruit shell carbon and be crushed to 8～12um；150g potassium hydroxide is dissolved in 100mL water, with fruit shell carbon
Mix homogeneously, is dried under vacuum；Then above-mentioned material is added in the activation furnace of nitrogen protection, with the ramp of 5 DEG C/min
To 800 DEG C and keep 2h；After being cooled to room temperature, activation products are washed to neutrality, are subsequently adding the hydrochloric acid reflux 2h of 6M, again
It is washed with deionized water to neutrality；Add the graphene oxide aqueous dispersions of 300mL0.6% concentration, and be added thereto to 2g trimerization
Cyanamide, ultrasonic agitation 1h, then it is spray-dried；Above-mentioned material is placed in reduction furnace, with 10 DEG C/min's under hydrogen shield
Ramp is to 800 DEG C and keeps 3h；Temperature i.e. obtains the shell base Supercapacitor carbon that Graphene is modified after being down to room temperature.
Detecting the modified shell base Supercapacitor carbon of above-described embodiment 3 preparation, specific surface area is 2250m2/g。
This activated carbon is mixed homogenate with binding agent SBR with CMC, is uniformly coated on aluminium foil, drying, roll, punching
After be assembled into ultracapacitor (organic system, 2.7V).
The ultracapacitor of above-described embodiment 3 preparation is carried out performance detection, when electric current density is 2A/g, mass ratio electricity
Hold for 145F/g.
Embodiment 4
Take 100g fruit shell carbon and be crushed to 8～12um；200g potassium hydroxide is dissolved in 100mL water, with fruit shell carbon
Mix homogeneously, is dried under vacuum；Then above-mentioned material is added in the activation furnace of nitrogen protection, with the ramp of 5 DEG C/min
To 800 DEG C and keep 2h；After being cooled to room temperature, activation products are washed to neutrality, are subsequently adding the hydrochloric acid reflux 2h of 6M, again
It is washed with deionized water to neutrality；Add the graphene oxide aqueous dispersions of 300mL0.6% concentration, and be added thereto to 2g trimerization
Cyanamide, ultrasonic agitation 1h, then it is spray-dried；Above-mentioned material is placed in reduction furnace, with 10 DEG C/min's under hydrogen shield
Ramp is to 800 DEG C and keeps 3h；Temperature i.e. obtains the shell base Supercapacitor carbon that Graphene is modified after being down to room temperature.
Detecting the modified shell base Supercapacitor carbon of above-described embodiment 4 preparation, specific surface area is 2420m2/g。
This activated carbon is mixed homogenate with binding agent SBR with CMC, is uniformly coated on aluminium foil, drying, roll, punching
After be assembled into ultracapacitor (organic system, 2.7V).
The ultracapacitor of above-described embodiment 4 preparation is carried out performance detection, when electric current density is 2A/g, mass ratio electricity
Hold for 160F/g.
Above a kind of compound active fruit shell carbon that the present invention provides and preparation method thereof, application are carried out detailed Jie
Continuing, principle and the embodiment of the present invention are set forth by specific case used herein, and the explanation of above example is only
It is the method and core concept thereof being adapted to assist in and understanding the present invention, including best mode, and also makes any skill of this area
Art personnel can put into practice the present invention, including manufacturing and using any device or system, and the method implementing any combination.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to this
Bright carrying out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.The present invention is special
Profit protection scope be defined by the claims, and those skilled in the art can be included it is conceivable that other embodiments.As
Really these other embodiments have the structural element being not different from claim character express, if or they include with power
The character express that profit requires is without the equivalent structural elements of essence difference, then these other embodiments also should be included in claim
In the range of.
Claims (10)
1. the preparation method of a compound active fruit shell carbon, it is characterised in that comprise the following steps:
A) the active fruit shell carbon powder after steam activation is mixed with alkali, then after overactivation, obtain activated carbon semi-finished product；
B) after activated carbon semi-finished product above-mentioned steps obtained mix again with graphene oxide solution, and reduction reaction is carried out,
Obtain compound active fruit shell carbon.
Preparation method the most according to claim 1, it is characterised in that described alkali includes potassium hydroxide, sodium hydroxide and hydrogen
One or more in calcium oxide；
Described active fruit shell carbon powder is 1:(0.5～2 with the mass ratio of alkali).
Preparation method the most according to claim 1, it is characterised in that the temperature of described activation is 600～950 DEG C, described
The time of activation is 0.5～4h.
Preparation method the most according to claim 1, it is characterised in that the granularity of described active fruit shell carbon powder is 8～12 μm；
The average sheet footpath of described graphene oxide is 1～50 μm；
It is 0.1%～1% that the quality of described graphene oxide accounts for the ratio of described active fruit shell carbon opaque amount.
Preparation method the most according to claim 1, it is characterised in that described reduction reaction is particularly as follows: at protective gas
Under conditions of carry out reduction reaction；
Described protective gas includes one or more in hydrogen, ammonia and nitrogen；
The temperature of described reduction reaction is 650～1200 DEG C, and the time of described reduction reaction is 1～6h.
Preparation method the most according to claim 1, it is characterised in that described step B) particularly as follows:
B`) after activated carbon semi-finished product, nitrogen source and graphene oxide solution above-mentioned steps obtained mixes again, and reduce
Reaction, obtains compound active fruit shell carbon.
Preparation method the most according to claim 6, it is characterised in that described nitrogen source includes tripolycyanamide and/or carbamide；
It is 1%～3% that the quality in described nitrogen source accounts for the ratio of described active fruit shell carbon opaque amount.
8. a compound active fruit shell carbon, it is characterised in that include active fruit shell carbon and be compounded in the graphene layer on its surface.
Compound active fruit shell carbon the most according to claim 8, it is characterised in that described compound active fruit shell carbon is by fruit
Shell activated carbon, graphene oxide and nitrogen source obtain after compound.
10. a ultracapacitor, it is characterised in that comprise the compound shell prepared by claim 1～7 any one and live
Compound active fruit shell carbon described in property charcoal or claim 8～9 any one.
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