CN105788885B - A kind of explosion method prepares the preparation method of camellia petal base sulphur, the technique of nitrogen co-doped fold carbon nanosheet and electrode of super capacitor - Google Patents
A kind of explosion method prepares the preparation method of camellia petal base sulphur, the technique of nitrogen co-doped fold carbon nanosheet and electrode of super capacitor Download PDFInfo
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Abstract
The invention belongs to the preparation field of biomass-based carbon material, the preparation method that a kind of explosion method prepares camellia petal base sulphur, the technique of nitrogen co-doped fold carbon nanosheet and electrode of super capacitor is specifically disclosed, the technique comprises the following steps：The pretreatment of raw material；Camellia petal base sulphur, the preparation of nitrogen co-doped fold carbon nanosheet：Nitrogen source, sulphur source and detonator are added in camellia petal powder after pretreatment and is well mixed, mixture is put into reactor, temperature is maintained at 700~900 DEG C, 1~3h of sustained response under inert gas shielding；The post processing of product.The present invention use the camellia petal with laminated structure for carbon source, add nitrogen source, sulphur source and the vigorous reaction that similar blast occurs under high temperature after detonator by the tear of camellia petal for carbon nanosheet while realize the carbonization of camellia petal and sulphur, nitrogen co-doped.Preparation method of the present invention is simple, and cost is low, and production efficiency is high and saves the energy, and product has good chemical property.
Description
Technical field
The invention belongs to the preparation field of biomass-based carbon material, and in particular to a kind of explosion method prepares camellia petal base
The preparation method of sulphur, the technique of nitrogen co-doped fold carbon nanosheet and electrode of super capacitor.
Background technology
Ultracapacitor is a kind of novel energy storage apparatus, it has, and specific capacitance is big, the charging interval is short, service life length,
The features such as good temp characteristic and environmental protection.It bridges the high-power output and battery/fuel cell of conventional electrostatic capacitor
High energy storage function, it is considered to be future ideality electrochmical power source, so having broad application prospects and huge warp
Ji benefit.In electrode material for super capacitor, earliest and most widely used is various forms of carbon materials.
Super capacitor carbon electrode material gradually develops into widely studied at present from the big activated carbon of earliest specific surface area
Carbon fiber, CNT and graphene etc..Graphene is a kind of two-dimentional carbon material, due to its unique two-dimensional structure, big
Therefore specific surface area, good electric conductivity are widely used and super capacitor, lithium battery, sode cell, lithium-air battery etc. are stored up
Can field.But limitation very big the shortcomings of the expensive of grapheme material, low yield, poor ductility, cumbersome preparation process
Its application in actual industrial.In recent years, it is also same with the carbon nanosheet similar to graphene-structured (thin slice Rotating fields)
Sample presents some physics and chemical property similar to graphene, such as has high conductance, big specific surface area, excellent
Chemical stability etc..Scientists significantly improve its machinery, conductive and electrification by introducing the miscellaneous element such as N, P, S
Learn performance.But the preparation of graphene is existed so far：A series of problems, such as cost height, complex process, unfriendly environment.
People's environmental consciousness, discarded object recycled the gradually reinforcement of consciousness in the last few years, and biomass carbon is used as ultracapacitor, lithium electricity etc.
Energy storage device electrode material is increasingly becoming study hotspot.
In the prior art, the method for preparing carbon nanosheet using biomass carbon is mainly PECVD and sunk
Area method, arc discharge method, template etc., not only equipment requirement is higher for these methods, and the yield of product is relatively low.In addition, material
The factor that the cost of material considers needed for being also.
Therefore develop a kind of raw material sources extensively, technique with low cost and simple and easy to apply come prepare with scale N, S or
Two kinds of element codope carbon nanosheets have very important application value.
The content of the invention
It is an object of the invention to provide the work that a kind of explosion method prepares camellia petal base sulphur, nitrogen co-doped fold carbon nanosheet
Skill and a kind of preparation method of the electrode of ultracapacitor, above-mentioned technique have simple, reproducible, with low cost, environment friend
Good the advantages of, and camellia petal base sulphur, the electrode of nitrogen co-doped fold carbon nanosheet and super capacitor prepared have it is good
Chemical property.
Above-mentioned purpose is to be achieved through the following technical solutions：A kind of explosion method prepares camellia petal base sulphur, nitrogen co-doped pleat
The technique of wrinkle carbon nanosheet, comprises the following steps：
(1)：The pretreatment of raw material：Camellia petal is cleaned, dried, mechanical crushing, then sieve；
(2)：Camellia petal base sulphur, the preparation of nitrogen co-doped fold carbon nanosheet：In camellia petal powder after pretreatment
Nitrogen source, sulphur source and detonator are added in end and is well mixed, mixture is put into reactor, temperature is maintained 700~900
DEG C, 1~3h of sustained response under inert gas shielding；
(3)：Camellia petal base sulphur, the post processing of nitrogen co-doped fold carbon nanosheet：Treat that temperature drop, to room temperature, takes out tea
Flower petal base sulphur, nitrogen co-doped fold carbon nanosheet, wash, dry.
The present invention uses the camellia petal with laminated structure for carbon source, using the special laminated structure of camellia petal, plus
It is carbon nanosheet by the tear of stratiform camellia petal to enter nitrogen source, sulphur source with the vigorous reaction that similar blast occurs under high temperature after detonator
While realize the carbonization of camellia petal and sulphur, nitrogen co-doped.The present invention uses explosion method, a step by the way of once heating
Above-mentioned technical purpose is realized, preparation method is simple, and cost is low, production efficiency is high and saves the energy.
Camellia petal base sulphur, nitrogen co-doped fold carbon nanosheet prepared by the present invention, in the carbon skeleton of porous carbon nanosheet
Middle introducing sulphur, nitrogen-atoms, graphite microcrystal plane layer produced many dislocations, bent, off normal etc. has unpaired electron
Defective bit；Sulphur, the introducing of nitrogen-atoms make material surface have alkalescence simultaneously, can reinforcing material surface wettability, raising material
Performance.Camellia petal base sulphur, the nitrogen co-doped fold carbon nanosheet prepared by present invention process, because it has high ratio surface
Product, with short ion transport distance and appropriate doping, therefore the material has good electrochemical energy storage performance, through surveying
Examination, its specific surface area reaches 1100~1500m2g-1, total pore volume is 0.61~0.91cm3g-1, sulfur content 0.6~2% is nitrogenous
Amount 2~5%；Test result indicates that, there is high specific capacitance, preferable fake capacitance, height using its electrode of super capacitor prepared
Cyclical stability, performance of the supercapacitor and most of nitrogen-doped porous carbon material of the performance better than commercial activated carbon.
Preferably, further technical scheme is：The nitrogen source, sulphur source and detonator are ammonium persulfate.Persulfuric acid
Ammonium decomposes to give off oxygen quickly as detonator in higher temperature, with the rise of temperature, and decomposition reaction speed is accelerated, high temperature
When reach explosion limit, with ammonium persulfate and its catabolite explosive reaction occurs for camellia petal, while realizing camellia petal
Carbonization and sulphur, nitrogen co-doped.
Further technical scheme is：The mass ratio of the camellia petal powder and ammonium persulfate is 1:0.5~1.5.
Further technical scheme is：The mass ratio of the camellia petal powder and ammonium persulfate is 1:1.
Further technical scheme is：The sulphur source is ammonium persulfate, and the nitrogen source is ammonium persulfate and other ammonium salts.Should
Work as understanding, other ammonium salts that can resolve into ammonia under the high temperature conditions can be as nitrogen source.
Further technical scheme is：The ammonium salt is the one or more in ammonium nitrate, percarbonic acid ammonium and ammonium hydrogen carbonate.
Ammonium nitrate, percarbonic acid ammonium and ammonium hydrogen carbonate high temperature easily decompose generation ammonia, and the ammonia of generation is easy to camellia flower in explosive reaction
N doping reaction occurs for valve.
Further technical scheme is：The detonator and nitrogen source are one in ammonium nitrate, percarbonic acid ammonium and ammonium persulfate
Plant or a variety of.Ammonium nitrate, percarbonic acid ammonium and ammonium persulfate, which are not only heated, easily to be decomposed, while during higher temperatures, being easily caused blast anti-
Should.
Further technical scheme is：Reaction temperature in the step (2) is 800 DEG C.Through lot of experiment validation, this is anti-
Should at a temperature of reaction product performance it is further preferred that.
Further technical scheme is：Reaction time in the step (2) is 2h.In this way, on the one hand ensureing reaction
Fully carry out, be on the other hand unlikely to the reaction time long and reduce economic benefit and efficiency.
Further technical scheme is：The inert gas is nitrogen or argon gas；
Further technical scheme is：The mesh number of sieving sieve used is 60 mesh in the step (1)；In this way, on the one hand
Ensure material fineness, be on the other hand unlikely to that particle diameter is too small and waste of materials.
Further technical scheme is：The step of having a compacting before mixture reaction in the step (2), in this way, can
Make the structure of the mixture relatively compact, explosive reaction could be occurred by being increased to after target temperature.It is pointed out that if
The mixture structure for participating in reaction is not fine and close, is increased to ammonium salt after some temperature and acutely decomposes, discharges a large amount of gases by space
It is middle freely to overflow, thus cause not reaching explosion limit and cause reaction to fail.
Further technical scheme is：The reactor is tube furnace.
To reach above-mentioned technical purpose, present invention also offers a kind of preparation method of the electrode of ultracapacitor, first
It is 1 by mass ratio:0.5~1.5:A kind of explosion method described in 7~9 conductive agent, binding agent and above-mentioned any one prepares tea
Camellia petal base sulphur, nitrogen co-doped fold carbon nanosheet prepared by flower petal base sulphur, the technique of nitrogen co-doped fold carbon nanosheet
Well mixed, addition solvent is tuned into muddy, is dried in the conductive substrates that above-mentioned slurry is coated on, in 10~20Mpa of pressure
Lower compacting, is prepared into electrode of super capacitor.
Preferably, further technical scheme is：The conductive agent includes acetylene black, carbon black, Delanium, natural stone
Ink, flake graphite, vapor phase method grown carbon fiber, CNT, metal dust and one kind in metallic fiber or it is any two kinds with
On combination.
Further technical scheme is：The binding agent include polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene,
Polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, polycyclic oxygen second
Dilute, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol and hydroxy propyl cellulose
One kind or any two or more combination in element.
Further technical scheme is：The solvent includes water, alcohols, polyalcohols, terpene, dimethyl carbonate, carbonic acid two
One kind or any two or more combination in ethyl ester, ethyl acetate and methyl propionate.
Further technical scheme is：The conductive agent is acetylene black, and the binding agent is polytetrafluoroethylene (PTFE), the solvent
For water, the conductive substrates are nickel foam.
Further technical scheme is：The conductive agent, binding agent and a kind of above-mentioned arbitrary explosion method prepare camellia flower
Valve base sulphur, the camellia petal base sulphur of the technique preparation of nitrogen co-doped fold carbon nanosheet, the matter of nitrogen co-doped fold carbon nanosheet
Amount is than being 1:1:8.
Further technical scheme is：The pressure is 15MPa.
Further technical scheme is：The method of the coating include dip-coating method, knife coating, spin-coating method, spraying process,
Silk screen print method and one kind in suspended particles dip coating or any two or more combination.
Further technical scheme is：The size of the conductive substrates is 1 square centimeter.
In summary, the present invention is raw material using camellia petal cheap and easy to get, using its special architectural feature, is passed through
Mix after simple pretreatment with nitrogen source, sulphur source and detonator, carries out being carbonized under inert gas shielding and sulphur, nitrogen co-doped,
Obtain camellia petal base sulphur, nitrogen co-doped fold carbon nanosheet with large specific surface area and superelevation pore volume.In addition, through reality
Checking, the motor of the ultracapacitor of preparation shows good chemical property and higher cycle efficieny ratio.The present invention
With low cost, technique is simple, is conducive to industrialization.
Brief description of the drawings
The accompanying drawing for constituting the part of the present invention is used for providing a further understanding of the present invention, schematic reality of the invention
Apply example and its illustrate to be used to explain the present invention, do not constitute inappropriate limitation of the present invention.
Fig. 1 is camellia petal base sulphur, nitrogen co-doped fold carbon nanosheet SEM and TEM figure in embodiment 1；
Fig. 2 is camellia petal base sulphur, nitrogen co-doped fold carbon nanosheet BET adsorption curve figures in embodiment 1；
Fig. 3 is camellia petal base sulphur, nitrogen co-doped fold carbon nanosheet XPS figures in embodiment 1；
Fig. 4 is camellia petal base sulphur, the electrode of super capacitor of nitrogen co-doped fold carbon nanosheet preparation in embodiment 1
Specific capacitance is with current density change curve map；
Fig. 5 is camellia petal base sulphur, nitrogen co-doped fold carbon nanosheet ultracapacitor cycle performance figure in embodiment 1；
Fig. 6 is camellia petal base sulphur, the test of nitrogen co-doped fold carbon nanosheet lithium battery high rate performance in embodiment 1.
Embodiment
The present invention will be described in detail below in conjunction with the accompanying drawings, and the description of this part is only exemplary and explanatory, should not
There is any restriction effect to protection scope of the present invention.In addition, description of the those skilled in the art according to this document, can be right
Feature in this document in embodiment and not in be the same as Example carries out respective combination.
Embodiment 1
To collect the camellia petal washing that the biomass material that comes withers dry, crush after cross 60 mesh sieves, take lower part of screen point.
Weigh 2g lower parts of screen point and 2g ammonium persulfates and milled while being put into agate and grinding in alms bowl, be allowed to be sufficiently mixed, homogeneous mixture is turned
Medication spoon compacting in magnetic boat is moved to, is put into tube furnace and is warming up to reaction target temperature under nitrogen protection, reacted, temperature
800 DEG C are maintained at, continues 2h, sulfur and nitrogen co-doped fold carbon nanosheet is formed.
By obtained camellia petal base sulphur, the washing drying of nitrogen co-doped fold carbon nanosheet.Its specific surface area reaches after tested
To 1500m2g-1, total pore volume is 0.91cm3g-1, sulfur content 2%, nitrogen content 5%；
From a, b in Fig. 1, this uniformity is can be seen that in the ESEM of different multiplying, and understand pleat
Rennet shape nanometer sheet is successfully synthesized out：Understood from c, d, can be seen that have in this nanometer sheet in different multiplying projection electron microscope
Many balloon-shaped structures, are conducive to increase specific surface area to improve chemical property.
Fig. 2 is Type-IV type nitrogen adsorption curves, provable camellia petal base sulphur, the nitrogen co-doped fold carbon nanosheet
Material has higher specific surface area, and with micropore and mesoporous distribution
Fig. 3 be camellia petal base sulphur, nitrogen co-doped fold carbon nanosheet XPS scheme, in the figure it can be seen that obvious sulphur,
The peak of nitrogen, it was demonstrated that the carbon nanosheet is successfully doped with nitrogen sulfur heteroatom.
Will be according to 1:1:The acetylene black of 8 ratios, polytetrafluoroethylene (PTFE), camellia petal base sulphur, the mixing of nitrogen co-doped carbon nanosheet
Uniformly, add water and be tuned into muddy, be uniformly applied in one square centimeter of nickel foam and dried using knife coating, 15Mpa compactings,
Prepare electrode of super capacitor.
After tested, the specific capacitance of the electrode of super capacitor of preparation is up to 275F g–1。
As shown in Figure 4, with the increase of current density, specific capacitance decreasing value is simultaneously little, i.e., should in the case where increasing current density
The electrode performance of electric capacity prepared by material does not have obvious decay, in 20A g-1Current density under, can still keep specific capacitance to reach
To 240F g–1Left and right, illustrates that camellia petal base sulphur, nitrogen co-doped carbon nanosheet have higher meso-hole structure, adds carbon materials
The contact area of material and point solution matter reduces the resistance of ion diffusion, so as to improve its capacitive property.
As shown in Figure 5, with the increase for recycling number of times, the decline of its capacity retention is not obvious, in circulation 10,000
Capacity retention is still 98% or so after secondary, it was demonstrated that the camellia petal base sulphur of the invention prepared, nitrogen co-doped fold carbon nanometer
The electrode of piece and ultracapacitor prepared therefrom has superior cycle performance.
In addition, the camellia petal base sulphur, the nitrogen co-doped fold carbon nanosheet that are prepared using the present invention are used as Anode of lithium cell
During material, obvious advantage is also embodied, as shown in fig. 6, this anode material first discharge specific capacity is up to 1600mAh/g,
Its specific capacity still has 200mAh/g under 10A/g high current densities, hence it is evident that better than commercial graphite electrode.
Embodiment 2
To collect the camellia petal washing that the biomass material that comes withers dry, crush after cross 60 mesh sieves, take lower part of screen point.
Weigh 2g lower parts of screen point and 2g ammonium persulfates and milled while being put into agate and grinding in alms bowl, be allowed to be sufficiently mixed, homogeneous mixture is turned
Medication spoon compacting in magnetic boat is moved to, is put into tube furnace and is warming up to reaction target temperature under nitrogen protection, reacted, temperature
700 DEG C are maintained at, continues 2h, sulfur and nitrogen co-doped fold carbon nanosheet is formed.
By obtained camellia petal base sulphur, the washing drying of nitrogen co-doped fold carbon nanosheet.Its specific surface area reaches after tested
To 1122m2g-1, total pore volume is 0.61cm3g-1。
Will be according to 1:1:The acetylene black of 8 ratios, polytetrafluoroethylene (PTFE), camellia petal base sulphur, the mixing of nitrogen co-doped carbon nanosheet
Uniformly, add water and be tuned into muddy, be uniformly applied in one square centimeter of nickel foam and dried using knife coating, 20Mpa compactings,
Prepare electrode of super capacitor.
After tested, the specific capacitance of the electrode of super capacitor of preparation is 229F g–1。
Embodiment 3
To collect the camellia petal washing that the biomass material that comes withers dry, crush after cross 60 mesh sieves, take lower part of screen point.
Weigh 2g lower parts of screen point and 2g ammonium persulfates and milled while being put into agate and grinding in alms bowl, be allowed to be sufficiently mixed, homogeneous mixture is turned
Medication spoon compacting in magnetic boat is moved to, is put into tube furnace and is warming up to reaction target temperature under nitrogen protection, reacted, temperature
900 DEG C are maintained at, continues 2h, sulfur and nitrogen co-doped fold carbon nanosheet is formed.
By obtained camellia petal base sulphur, the washing drying of nitrogen co-doped fold carbon nanosheet.Its specific surface area reaches after tested
To 1563m2g-1, total pore volume is 0.95cm3g-1, it is necessary to explanation, product yield is very low under the conditions of this, 10% with
Under.
Will be according to 1:1:The acetylene black of 8 ratios, polytetrafluoroethylene (PTFE), camellia petal base sulphur, the mixing of nitrogen co-doped carbon nanosheet
Uniformly, add water and be tuned into muddy, be uniformly applied in one square centimeter of nickel foam and dried using dip-coating method, 10Mpa
Compacting, prepares electrode of super capacitor.
After tested, the specific capacitance of the electrode of super capacitor of preparation is 174F g–1。
Embodiment 4
To collect the camellia petal washing that the biomass material that comes withers dry, crush after cross 60 mesh sieves, take lower part of screen point.
Weigh 2g lower parts of screen point and 1g ammonium persulfates and milled while being put into agate and grinding in alms bowl, be allowed to be sufficiently mixed, homogeneous mixture is turned
Medication spoon compacting in magnetic boat is moved to, is put into tube furnace and is warming up to reaction target temperature under argon gas protection, reacted, temperature
800 DEG C are maintained at, continues 2h, sulfur and nitrogen co-doped fold carbon nanosheet is formed.
By obtained camellia petal base sulphur, the washing drying of nitrogen co-doped fold carbon nanosheet.Its specific surface area reaches after tested
To 659m2g-1, total pore volume is 0.36cm3g-1。
Will be according to 1:1:The acetylene black of 8 ratios, polytetrafluoroethylene (PTFE), camellia petal base sulphur, the mixing of nitrogen co-doped carbon nanosheet
Uniformly, add water and be tuned into muddy, be uniformly applied in one square centimeter of nickel foam and dried using silk screen print method, 15Mpa
Compacting, prepares electrode of super capacitor.
After tested, the specific capacitance of the electrode of super capacitor of preparation is 162F g–1。
Embodiment 5
To collect the camellia petal washing that the biomass material that comes withers dry, crush after cross 60 mesh sieves, take lower part of screen point.
Weigh 2g lower parts of screen point and 3g ammonium persulfates and milled while being put into agate and grinding in alms bowl, be allowed to be sufficiently mixed, homogeneous mixture is turned
Medication spoon compacting in magnetic boat is moved to, is put into tube furnace and is warming up to reaction target temperature under argon gas protection, reacted, temperature
800 DEG C are maintained at, continues 1h, sulfur and nitrogen co-doped fold carbon nanosheet is formed.
By obtained camellia petal base sulphur, the washing drying of nitrogen co-doped fold carbon nanosheet.Industry tests its specific surface area
Reach 1122m2g-1, total pore volume is 0.62cm3g-1, it is necessary to explanation, product yield is very low under the conditions of this, 10% with
Under.
Will be according to 1:0.5:The acetylene black of 8 ratios, polytetrafluoroethylene (PTFE), camellia petal base sulphur, nitrogen co-doped carbon nanosheet are mixed
Close uniform, add water and be tuned into muddy, be uniformly applied in one square centimeter of nickel foam and dried using suspended particles dip coating,
10Mpa is compacted, and prepares electrode of super capacitor.
After tested, the specific capacitance of the electrode of super capacitor of preparation is 195F g–1。
Embodiment 6
To collect the camellia petal washing that the biomass material that comes withers dry, crush after cross 60 mesh sieves, take lower part of screen point.
Weigh 2g lower parts of screen point, 2g percarbonic acids ammonium and 0.5g ammonium persulfates and milled while being put into agate and grinding in alms bowl, be allowed to be sufficiently mixed, will
Homogeneous mixture is transferred to medication spoon compacting in magnetic boat, is put into tube furnace and is warming up to reaction target temperature under nitrogen protection,
Reacted, temperature is maintained at 800 DEG C, continue 2h, form sulfur and nitrogen co-doped fold carbon nanosheet.
By obtained camellia petal base sulphur, the washing drying of nitrogen co-doped fold carbon nanosheet.Its specific surface area reaches after tested
To 1012m2g-1, total pore volume is 0.58cm3g-1。
Will be according to 1:1.5:The acetylene black of 7 ratios, polytetrafluoroethylene (PTFE), camellia petal base sulphur, nitrogen co-doped carbon nanosheet are mixed
Close uniform, add water and be tuned into muddy, be uniformly applied in one square centimeter of nickel foam and dried using spraying process, 15Mpa pressures
It is real, prepare electrode of super capacitor.
After tested, the specific capacitance of the electrode of super capacitor of preparation is 155F g–1。
Embodiment 7
To collect the camellia petal washing that the biomass material that comes withers dry, crush after cross 60 mesh sieves, take lower part of screen point.
Weigh 2g lower parts of screen point, 2g ammonium nitrate and 0.5g ammonium persulfates and milled while being put into agate and grinding in alms bowl, be allowed to be sufficiently mixed, will be equal
Even mixture is transferred to medication spoon compacting in magnetic boat, is put into tube furnace and is warming up to reaction target temperature under nitrogen protection, enters
Row reaction, temperature is maintained at 800 DEG C, continues 2h, forms sulfur and nitrogen co-doped fold carbon nanosheet.
By obtained camellia petal base sulphur, the washing drying of nitrogen co-doped fold carbon nanosheet.Its specific surface area reaches after tested
To 1368m2g-1, total pore volume is 0.88cm3g-1。
Will be according to 1:1:The acetylene black of 9 ratios, polytetrafluoroethylene (PTFE), camellia petal base sulphur, the mixing of nitrogen co-doped carbon nanosheet
Uniformly, add water and be tuned into muddy, be uniformly applied in one square centimeter of nickel foam and dried using spin-coating method, 15Mpa compactings,
Prepare electrode of super capacitor.
After tested, the specific capacitance of the electrode of super capacitor of preparation is 212F g–1。
Embodiment 8
To collect the camellia petal washing that the biomass material that comes withers dry, crush after cross 60 mesh sieves, take lower part of screen point.
Weigh 2g lower parts of screen point, 1g ammonium hydrogen carbonate and 1g ammonium persulfates and be put into agate and grind in alms bowl and mill, be allowed to be sufficiently mixed, will uniformly mix
Compound is transferred to medication spoon compacting in magnetic boat, is put into tube furnace and is warming up to reaction target temperature under argon gas protection, carries out anti-
Should, temperature is maintained at 800 DEG C, continues 1h, forms sulfur and nitrogen co-doped fold carbon nanosheet.
By obtained camellia petal base sulphur, the washing drying of nitrogen co-doped fold carbon nanosheet.Its specific surface area reaches after tested
To 1321m2g-1, total pore volume is 0.83cm3g-1。
Will be according to 1:1:Conductive agent (acetylene black, carbon black, Delanium, native graphite, flake graphite, the vapor phase method of 8 ratios
One kind in grown carbon fiber, CNT, metal dust and metallic fiber is any two or more), binding agent (tetrafluoro second
Alkene, Kynoar, polyethylene, polypropylene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene rubber
Glue, polybutadiene, fluorubber, dilute polycyclic oxygen second, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, ring
One kind in oxygen tree fat, polyvinyl alcohol and hydroxypropyl cellulose or any two or more combination), camellia petal base sulphur, nitrogen it is common
The carbon nanosheet that adulterates is well mixed, and adds solvent (water, alcohols, polyalcohols, terpene, dimethyl carbonate, diethyl carbonate, acetic acid
One kind or any two or more combination in ethyl ester and methyl propionate) muddy is tuned into, uniformly smeared using silk screen print method
Dried in one square centimeter of nickel foam, 15Mpa compactings prepare electrode of super capacitor.
After tested, the specific capacitance of the electrode of super capacitor of preparation is 210~227F g–1。
Camellia petal base sulphur, nitrogen co-doped fold carbon nanosheet property representation
Camellia petal base sulphur, the structural characterization of nitrogen co-doped fold carbon nanosheet pass through N2Adsorb (Micromeritics
TriStar II 3020) test.Specific surface area is according to Brunauer-Emmett-Teller (BET) theoretical calculation, pore-size distribution
(PSD) propped up using the absorption of adsorption isotherm and use Barrett-Joyner-Halenda (BJH) model to calculate.
Camellia petal base sulphur, nitrogen co-doped carbon nanosheet are the method for testing for the electrode that raw material prepares ultracapacitor
The capacitive property of single electrode is tested using CHI760D electrochemical workstation three-electrode systems, wherein to electrode
For platinum electrode, Hg/HgO is reference electrode, and 6M KOH solutions are electrolyte.This example mainly using cyclic voltammetry (CV),
The method such as constant current charge-discharge (GC) and electrochemical impedance spectroscopy (EIS) carries out electrochemical property test.The circulation of single electrode
Volt-ampere test voltage range set is -1~0V.The current density of charge-discharge test is arranged on 0.5~20A g-1, and voltage range
For -1~0V.The specific capacitance of carbon material is calculated by the electric discharge branch of constant current charge-discharge according to below equation：
C=I/ (mdV/dt)
Wherein I is constant current, and m is the quality of active material, and dV/dt is according to the discharge curve for removing voltage drop part
Slope obtained by calculating.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (21)
1. a kind of explosion method prepares camellia petal base sulphur, the technique of nitrogen co-doped fold carbon nanosheet, it is characterised in that including such as
Lower step：
(1)：The pretreatment of raw material：Camellia petal is cleaned, dried, mechanical crushing, then sieve；
(2)：Camellia petal base sulphur, the preparation of nitrogen co-doped fold carbon nanosheet：In camellia petal powder after pretreatment
Add nitrogen source, sulphur source and detonator and be well mixed, will be put into after mixture compacted in reactor, maintain temperature 700~900
DEG C, 1~3h of sustained response under inert gas shielding；
(3)：Camellia petal base sulphur, the post processing of nitrogen co-doped fold carbon nanosheet：Temperature drop is treated to room temperature, camellia flower is taken out
Valve base sulphur, nitrogen co-doped fold carbon nanosheet, wash, dry.
2. a kind of explosion method according to claim 1 prepares camellia petal base sulphur, the work of nitrogen co-doped fold carbon nanosheet
Skill, it is characterised in that the nitrogen source, sulphur source and detonator are ammonium persulfate.
3. a kind of explosion method according to claim 2 prepares camellia petal base sulphur, the work of nitrogen co-doped fold carbon nanosheet
Skill, it is characterised in that the mass ratio of the camellia petal powder and ammonium persulfate is 1:0.5~1.5.
4. a kind of explosion method according to claim 3 prepares camellia petal base sulphur, the work of nitrogen co-doped fold carbon nanosheet
Skill, it is characterised in that the mass ratio of the camellia petal powder and ammonium persulfate is 1:1.
5. a kind of explosion method according to claim 1 prepares camellia petal base sulphur, the work of nitrogen co-doped fold carbon nanosheet
Skill, it is characterised in that the sulphur source is ammonium persulfate, the nitrogen source is ammonium persulfate and other ammonium salts.
6. a kind of explosion method according to claim 5 prepares camellia petal base sulphur, the work of nitrogen co-doped fold carbon nanosheet
Skill, it is characterised in that the ammonium salt is the one or more in ammonium nitrate, percarbonic acid ammonium and ammonium hydrogen carbonate.
7. a kind of explosion method according to claim 1 prepares camellia petal base sulphur, the work of nitrogen co-doped fold carbon nanosheet
Skill, it is characterised in that the detonator and nitrogen source are the one or more in ammonium nitrate, percarbonic acid ammonium and ammonium persulfate.
8. a kind of explosion method according to claim 1~7 any one prepares camellia petal base sulphur, nitrogen co-doped fold carbon
The technique of nanometer sheet, it is characterised in that the reaction temperature in the step (2) is 800 DEG C.
9. a kind of explosion method according to claim 8 prepares camellia petal base sulphur, the work of nitrogen co-doped fold carbon nanosheet
Skill, it is characterised in that the reaction time in the step (2) is 2h.
10. a kind of explosion method according to claim 1 prepares camellia petal base sulphur, the work of nitrogen co-doped fold carbon nanosheet
Skill, it is characterised in that the inert gas is nitrogen or argon gas.
11. a kind of explosion method according to claim 1 prepares camellia petal base sulphur, the work of nitrogen co-doped fold carbon nanosheet
Skill, it is characterised in that the mesh number of sieving sieve used is 60 mesh in the step (1).
12. a kind of explosion method according to claim 1 prepares camellia petal base sulphur, the work of nitrogen co-doped fold carbon nanosheet
Skill, it is characterised in that the reactor is tube furnace.
13. a kind of preparation method of the electrode of ultracapacitor, it is characterised in that by mass ratio be 1:0.5~1.5:7~9
A kind of explosion method described in conductive agent, binding agent and claim 1~12 any one prepares camellia petal base sulphur, nitrogen co-doped
Camellia petal base sulphur, the nitrogen co-doped fold carbon nanosheet of the technique preparation of fold carbon nanosheet are well mixed, and addition solvent is adjusted
Into muddy, dried in the conductive substrates that above-mentioned slurry is coated on, be compacted under 10~20Mpa of pressure, be prepared into super electricity
Container electrode.
14. a kind of preparation method of the electrode of ultracapacitor according to claim 13, it is characterised in that the conduction
Agent includes acetylene black, carbon black, Delanium, native graphite, flake graphite, vapor phase method grown carbon fiber, CNT, metal powder
End and one kind in metallic fiber or any two or more combination.
15. a kind of preparation method of the electrode of ultracapacitor according to claim 13, it is characterised in that the bonding
Agent include polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins,
Styrene butadiene ribber, polybutadiene, fluorubber, dilute polycyclic oxygen second, polyvinylpyrrolidone, polyester resin, acrylic acid tree
One kind or any two or more combination in fat, phenolic resin, epoxy resin, polyvinyl alcohol and hydroxypropyl cellulose.
16. a kind of preparation method of the electrode of ultracapacitor according to claim 13, it is characterised in that the solvent
Including one kind in water, alcohols, polyalcohols, terpene, dimethyl carbonate, diethyl carbonate, ethyl acetate and methyl propionate or appoint
The two or more combination of meaning.
17. a kind of preparation method of the electrode of ultracapacitor according to claim 13, it is characterised in that the conduction
Agent is acetylene black, and the binding agent is polytetrafluoroethylene (PTFE), and the solvent is water, and the conductive substrates are nickel foam.
18. a kind of preparation method of the electrode of ultracapacitor according to claim 17, it is characterised in that the conduction
A kind of explosion method described in agent, binding agent and claim 1~12 any one prepares camellia petal base sulphur, nitrogen co-doped fold
The camellia petal base sulphur of technique preparation, the mass ratio of nitrogen co-doped fold carbon nanosheet of carbon nanosheet are 1:1:8.
19. a kind of preparation method of the electrode of ultracapacitor according to claim 18, it is characterised in that the pressure
For 15MPa.
20. a kind of preparation method of the electrode of ultracapacitor according to claim 19, it is characterised in that the coating
Method include dip-coating method, knife coating, spin-coating method, spraying process, silk screen print method and suspended particles dip coating in one kind
Or any two or more combination.
21. a kind of preparation method of the electrode of ultracapacitor according to claim 13~19 any one, its feature
It is, the size of the conductive substrates is 1 square centimeter.
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