CN107265433A - Three-dimensional porous nitrating carbon material and its preparation method and application - Google Patents
Three-dimensional porous nitrating carbon material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to three-dimensional porous nitrating carbon material and its preparation method and application, methods described includes：Organic carbon source and metal tin-salt solution are added in organic solvent, is dried after being stirred 30~120 minutes at 40~80 DEG C, obtains the presoma containing metal pink salt and organic carbon source；Presoma of the gained containing tin metal pink salt and organic carbon source is placed in the atmosphere containing gas phase carbon source, CVD carbonizations heat treatment 10 minutes~12 hours is carried out at 300~1000 DEG C, then obtain after acid etch three-dimensional porous nitrating carbon material.The present invention is first by metal pink salt and vapour deposition process（CVD）With reference to three-dimensional porous nitrating carbon powder material is prepared, its technique is simple, with low cost, and controllability is strong, reproducible, it is easy to accomplish large-scale production.
Description
Technical field
The present invention relates to a kind of three-dimensional porous nitrating carbon material raw powder's production technology, more particularly to a kind of chemical gaseous phase
The method that deposition prepares the controllable three-dimensional porous toner body in aperture, belongs to Material Field.
Background technology
With the development of science and technology, environmental problem is increasingly becoming focus of attention, main to include three aspects：Air is dirty
Dye, water pollution, soil pollution.The discharge of carbon dioxide isothermal chamber gas causes global warming, sea particularly in air
A series of problems, such as plane rising, species extinction.Problems, which all originate from the mankind, can not effectively utilize the energy, so to the energy
It is efficient, inexpensive utilization and storage turn into 21st century human development hot issue, extensive pass is caused in the whole world
Note.All circles are enjoyed to favor as the lithium battery and ultracapacitor of green energy-storing mode, special super capacitor has due to it
Power density is big, and energy density is moderate, safe operation, has extended cycle life, green energy-storage system, has attracted vast institute of section to study
Personnel and the extensive concern of department of national governments, are with a wide range of applications.Porous carbon materials have light weight, compare surface
Product is big, toughness is high, modulus is high, stability is good, heatproof is high, the premium properties such as acid and alkali-resistance, nontoxic, adsorption capacity are good, easy to process,
It is thus of interest by various fields.In recent years, the development speed of carbon material subject was very fast, particularly in novel green storage
Can device --- research and application in ultracapacitor.Porous carbon materials be can as ultracapacitor core component storage
Can material.With other electrode materials, graphene, metal oxide, metal sulfide etc. are compared, carbon material preparation convenience,
Cycle is short, cheap.The independent support electrode of ultracapacitor need to have higher mechanical strength and big electric capacity, and three-dimensional
Porous carbon materials have high toughness, modulus height, stability is good, heatproof is high, chemically stable good, these premium properties make porous carbon
Material and porous carbon sill of sheet turn into electrode material for super capacitor very strong competitor.Chen delivered one equal to 2009
By carbon source of sucrose with preparing mesopore carbosphere by hydrothermal synthesis method after ethanol and deionized water blending, when it is applied to super
Specific capacity is up to 251F/g in capacitor.Recently, it is that template is prepared for spherical mesopore with silica gel and cellular glass to have researcher
Carbon material, talks presoma phenol and cetylamine and polymerize in the space of silica gel, being handled through superheat, be carbonized, removing template
Mesoporous carbon materials are obtained etc. step.Also it is template using commercial silica sol nano-particle to have researcher, and resorcinol and formaldehyde are
Carbon source prepares mesoporous carbon.But the early porous carbon materials preparation process Program of these traditional templates is cumbersome, it is necessary to first close
Into template, it is difficult to control the macroporous structure of material, and carbon source easily deposits the non-porous carbon material of generation.As can be seen here, it is how real
Existing low cost, method are simple, the adjustable three-dimensional porous carbon materials preparation method for material in aperture is particularly important.
From the preparation method of porous carbon materials, mainly there are catalytic activation method, a template, organic gel carbonization method and poly-
Compound blending carbonizatin method etc..Catalytic activation method prepares carbon materials blanking aperture and is difficult to control to, but template can prepare orderly Jie
Hole carbon material, but can cause the introducing of oxygen-containing functional group, causes its electric conductivity bad, and it is cumbersome to there is preparation procedure, mould
The problems such as plate is difficult to remove, in organic gel method, carbon source easily deposits the non-porous carbon material of generation, and research discovery utilizes metallic tin
Salt is mixed with organic carbon source presoma, then can obtain the adjustable porous carbon materials in aperture by a series of processing such as carbonizations.Though
So currently there are many kinds to prepare the method for porous carbon materials, but be due to that current various methodologies program is cumbersome, the high grade of price lacks
Point, is difficult to realize large-scale production.
Research finds that preparing porous carbon materials using metal pink salt needs to select suitable metal pink salt.Utilize nickel, iron etc.
Metal pink salt prepares three-dimensional porous carbon material and widely studied, but does not utilize also the metal pink salt of tin to prepare porous carbon
The relevant report of material.
The content of the invention
Based on this, an object of the present invention is to provide a kind of method that can simply prepare three-dimensional porous carbon material,
And make obtained three-dimensional porous nitrating carbon material that there is good electric conductivity and stability, abundant conductive network structure, big
Specific surface area, aperture is adjustable, suitable pore-size distribution, the need for meeting ultracapacitor field.
On the one hand, the invention provides a kind of method for preparing three-dimensional porous nitrating carbon material, including：
Organic carbon source and metal tin-salt solution are added in organic solvent, done after being stirred 30~120 minutes at 40~80 DEG C
It is dry, obtain the presoma containing metal pink salt and organic carbon source；
Presoma of the gained containing metal pink salt and organic carbon source is placed in the atmosphere containing gas phase carbon source, 300~1000
CVD carbonizations heat treatment 10 minutes~12 hours is carried out at DEG C, then obtains after acid etch three-dimensional porous nitrating carbon material.
The present invention first combines metal pink salt and chemical vapour deposition technique (CVD), i.e., in chemical vapor deposition processes
In, metal pink salt is introduced as pore creating material, prepares three-dimensional porous nitrating carbon powder material.Specifically, it is of the invention by metallic tin
Salting liquid is added in organic carbon source, and due to containing oxygen-containing functional group in organic carbon source, tin ion can be with containing in organic carbon source
Oxygen functional groups, such tin ion can be evenly distributed in organic carbon source.CVD (the chemical vapor depositions at 300~1000 DEG C
Product) during, organic carbon source can be cracked, and the oxygen and hydrogen in oxygen-containing functional group can depart from, and become water (H2O) vapor away,
Leave behind carbon.Certain graphited carbon is so formed, and tin ion is easy to be reduced (such as by hydrogen, carbon reduction) into tin
Simple substance, but because tin simple substance (one ran of granular size) is not easy to grow up at high temperature, such tin simple substance is just uniform
It is distributed in carbon.So after tin simple substance is etched (watery hydrochloric acid reacts with tin simple substance), hole will be produced.In super capacitor
This hole can provide high-specific surface area in device, electrolyte diffusion can fully be improved, so as to improve capacity of super capacitor.This work
Skill is simple, with low cost, and controllability is strong, reproducible, it is easy to accomplish large-scale production.Obtained three-dimensional porous nitrating carbon materials
Material, aperture can be in interior regulation and control in a big way, and specific surface area is big, up to 2000m2/ g, electric conductivity is good, is ultracapacitor
Suitable material.
It is preferred that the organic carbon source is selected from polyethylene glycol, polyvinylpyrrolidone, agar, melamine, sucrose and Portugal
At least one of grape sugar.
It is preferred that the organic solvent is selected from least one of methanol, ethanol and propyl alcohol, preferably ethanol, it is described to have
The mass ratio of machine carbon source and organic solvent is (2~20)：1, preferably (5~10)：1.
It is preferred that in the oxide of the metal pink salt selected from metallic tin, chloride, nitrate, oxalates, acetate
At least one, the concentration of the metal tin-salt solution is 0.1~5mol/L, preferably 0.5~2mol/L.
It is preferred that the volume ratio of the organic solvent and metal tin-salt solution is (2~30)：1, be preferably (6~10)：1.
It is preferred that the temperature of the CVD carbonizations heat treatment is 500~900 DEG C, the time is 10 minutes~10 hours, preferably
For 3~10 hours.
It is preferred that the atmosphere that the CVD carbonizations heat treatment is passed through includes：Below gas phase carbon source 100sccm, preferably 10~
50sccm；Below gas phase nitrogen source 100sccm, preferably 50~80sccm；10~100sccm of hydrogen, preferably 20~50sccm；Protection
20~800sccm of gas, preferably 20~400sccm.Also, it is preferred that the gas phase carbon source be selected from methane, acetylene, ethene, ethane,
At least one of propane and propylene；The nitrogen source is ammonia；It is described protection gas in argon gas, nitrogen and helium at least one
Kind.Wherein, chemical vapor deposition is exactly CVD processes, is referred specifically to：(typical temperature is more than 900 DEG C), organic carbon source at high temperature
It can crack, the oxygen and hydrogen in oxygen-containing functional group can depart from, and become water (H2O) vapor away, leave behind carbon, and this process
It is to be carried out under the atmosphere containing methane, methane can crack generation carbon radicals and hydroperoxyl radical when higher than 650 DEG C, and hydrogen is certainly
It can be converted on water, the what is said or talked about presoma that carbon radicals can be after cracking and deposited combined with the oxygen in organic carbon source by base, become stone
Black alkene.Graphene can be also produced in the case of no carbon source (for example, methane etc.), because organic carbon source is in cracking process
In, carbon can be combined freely, can also become graphene, but defect is relatively more, and degree of graphitization is relatively low.Nitrogen is used as protection
Gas, will not react with carbon material under the conditions of 1000 DEG C.
It is preferred that when carrying out CVD carbonization heat treatments, also importing other organic nitrogen sources and/or can to introduce other heteroatomic
Doped source, other described valuable nitrogen sources are melamine, and other described hetero atoms are P, O, S or B, and the doped source is selected from, thiophene
At least one of fen, pyrroles, borine, boron oxide, five phosphorous oxides, phosphorus chloride and boric acid, the N and other foreign atoms rub
You should be less than the 20% of carbon material carbon atom integral molar quantity at amount sum, namely heteroatom accounting is less than 20%.
It is preferred that carrying out acid etch using at least one of sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, nitric acid acid solution.
On the other hand, three-dimensional porous nitrating carbon material is prepared according to the above method present invention also offers one kind.Described three
The microscopic pattern for tieing up porous nitrating carbon material is three-dimensional network macroporous structure, and macropore diameter is distributed as 100nm~1 μm, and
(its distribution can be for (its distribution can be 2~50nm) also mesoporous in macroporous structure and microcellular structure<2μm).
Another further aspect, present invention also offers the above-mentioned three-dimensional porous nitrating carbon material of one kind in ultracapacitor and lithium ion
Application in battery device.
Compared with prior art, the invention has the advantages that：
Metal pink salt and vapour deposition process (CVD) are combined prepare three-dimensional porous nitrating carbon powder material first by the present invention, are had
For body, gel is obtained in the ethanol for being first dissolved in PEG-10000 (PEG-6000 0) and stannous chloride, after drying
With CVD, carbonization carbon matrix precursor (cracks organic carbon source, formation within the scope of certain temperature and under certain atmosphere again
Carbon simple substance, and gas phase carbon source and reducibility gas react and also form carbon simple substance), afterwards by the block grinding after carbonization simultaneously
With the salt acid etch metallic tin in the range of finite concentration, three-dimensional porous nitrating carbon dust is finally obtained.This technique is simple, and cost is low
Honest and clean, controllability is strong, reproducible, it is easy to accomplish large-scale production.Obtained three-dimensional porous nitrating carbon material, aperture can be larger
In the range of regulate and control, specific surface area is big, up to 2000m2/ g, electric conductivity is good, is the suitable material of ultracapacitor.
Brief description of the drawings
Fig. 1 shows the three-dimensional porous nitrating carbon material PN-900 prepared according to the methods of the invention of embodiment 1 scanning electricity
Mirror photo and transmission electron microscope photo；
Fig. 2 shows nitrogen adsorption desorption curve during metal pink salt various concentrations, and wherein P0.5-900 represents metallic tin salinity
For 0.5 mole every liter, chemical vapor deposition temperature is 900 DEG C, and it is 1 mole every liter that P1-900, which represents metallic tin salinity, chemistry
The temperature that is vapor-deposited is 900 DEG C, and it is 2 moles every liter that P2-900, which represents metallic tin salinity, and chemical vapor deposition temperature is 900
℃；
Fig. 3 shows the Raman spectrogram of three-dimensional porous carbon material prepared according to the methods of the invention, wherein Raman frequency shift scope
From 1000 to 3000cm-1, the position at three peaks is substantially on Raman spectrogram：D peaks 1340cm-1, G peaks 1591cm-1, wherein P1-
900 be three-dimensional porous without nitrogen-doped carbon material, and PN-900 is three-dimensional porous nitrogen-doped carbon material；
Fig. 4 shows the BET test collection of illustrative plates for the three-dimensional porous nitrating carbon material powder that the method according to the invention is prepared, wherein
P1-900 is to be three-dimensional porous without nitrogen-doped carbon material, and PN-900 is three-dimensional porous nitrogen-doped carbon material, (a) figure be nitrogen adsorption-
Desorption curve, (b) figure is pore size distribution curve；
Fig. 5 shows three-dimensional porous nitrating carbon material powder PN-900 prepared according to the methods of the invention as super capacitor equipment
The capacitive property test chart of material, wherein, (a) figure is the capacitive property under different scanning rates that cyclic voltammetry is measured, (b)
Figure is the constant current charge-discharge performance under different size charging and discharging currents；
Fig. 6 shows three-dimensional porous nitrating carbon material powder PN-900 prepared according to the methods of the invention as ultracapacitor device
The power of part performance-energy curve figure；
Fig. 7 is the three-dimensional porous Raman collection of illustrative plates without nitrogen-doped carbon material for preparing under different carburizing temperatures.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments
The present invention is merely to illustrate, is not intended to limit the present invention.
Present invention uses a kind of new method, metal pink salt and organic carbon source are mixed to get carbon Gel Precursor, then
Three-dimensional porous nitrating carbon material powder is thermally treated resulting under certain atmosphere and in certain temperature range with reference to CVD method.This
Planting three-dimensional porous nitrating carbon material has abundant pore-size distribution (macropore, mesoporous, micropore), with very big specific surface area, and
And when metallic tin salinity can realize the regulation and control to pore-size distribution within the specific limits, excellent electric conductivity, abundant leads
Electric network structure, and after suitable activation, more possessing the steady pore-size distribution put and be adapted to of abundant activity, so as to have
There is outstanding performance of the supercapacitor.
The invention provides method that is a kind of novel and simply preparing three-dimensional porous carbon material, with reference to the life of CVD nitratings
Length obtains three-dimensional porous nitrating carbon material, and with bigger serface, high conductivity is suitable as super capacitor material.Below
Exemplarily illustrate the preparation method for the three-dimensional porous nitrating carbon material that the present invention is provided.
Organic carbon source is mixed with metal tin-salt solution, dried afterwards, then by CVD heat-treating methods, obtains netted
Nitrating carbon material and etch metal simple-substance, obtain three-dimensional porous nitrating carbon material powder.
In the present invention, as long as organic carbon source is nontoxic, and heating will not produce toxic gas and can serve as carbon
Presoma, including but not limited to PEG-6000 0 (PEG-10000), polyvinylpyrrolidone (pvp), sucrose, trimerization
The dusty materials such as cyanamide, glucose sugar.
Metal pink salt is nontoxic typically from cheap, physicochemical properties stabilization, and environment is not resulted in
The metal pink salt of threat, concentration is 0.1~5.0mol/L, preferably 0.5~2.0mol/L.By regulating and controlling metallic tin salinity,
The pore-size distribution and specific surface area of three-dimensional porous nitrating carbon material can be regulated and controled.In addition, by changing nitrogen source flow, can regulate and control
Nitrogen content is distributed in three-dimensional porous nitrating carbon material.Further, it is also possible to adjust carburizing temperature, thus it is possible to vary this three-dimensional porous nitrating
The degree of graphitization of carbon material.Therefore three-dimensional porous nitrating carbon material can be finally made in a variety of control measures.
Organic carbon source and metal tin-salt solution are added in ethanol solution, certain time is stirred.The organic carbon source can
Suitably select as requested.The mass ratio of the organic carbon source and organic solvent can be (2~20)：1, preferably (5~10)：1.
In the present invention, the organic carbon source that can be used include polyethylene glycol, polyvinylpyrrolidone, agar, melamine, sucrose,
At least one of glucose, metal pink salt may also include other metal oxides, metal chloride, metal nitrate and metal
Various oxides such as oxalates and combinations thereof, wherein metal oxide includes but is not limited to aluminum oxide, magnesia, zinc oxide, oxygen
Change at least one of titanium, barium monoxide, lead oxide etc., metal chloride includes but is not limited in stannous chloride, nickel chloride etc.
One kind, one kind that metal nitrate includes but is not limited in nickel nitrate, cobalt nitrate, ferrous nitrate etc., metal oxalate include but
It is not limited to one kind in nickel oxalate, ferric oxalate etc..
Solvent in metal salt solution can be the ethanol solution of any ratio.The concentration of the metal salt solution can for 0.1~
5.0mol/L, preferably 0.5~2.0mol/L.The volume ratio of organic solvent and the metal tin-salt solution can be (2~30)：1,
Preferably (6~10)：1.The amount ratio (mol ratio) of organic carbon source and the material of metal pink salt can be 2~10, preferably 3~5.Forerunner
Preparation of the liquid solution concentration to three-dimensional porous nitrating carbon material has a major impact.Excessive concentration or it is too low be unfavorable for it is three-dimensional porous
The preparation of nitrating carbon material.
Organic carbon source and metal tin-salt solution in a solvent, are stirred at 10-80 DEG C, mixing time can for 5min~
300min, preferably 30~120min.After the completion of stirring, gel is obtained after drying.Drying temperature can be 20~120 DEG C, preferably 30
~80 DEG C, drying time can be 1~96 hour, preferably 12~24 hours.As an example, by organic carbon source and finite concentration
Metal tin-salt solution mixing be added in organic solvent, stirring and dissolving, dry, heat treatment, be prepared into containing metal pink salt with
The presoma of organic carbon source.
After drying, gel is subjected to CVD carbonizations and is heat-treated, organic carbon source is cracked, three-dimensional porous nitrating carbon material is made.
During CVD carbonization heat treatments (heat treatment), temperature can be 300~1000 DEG C, preferably 500~900 DEG C, the time for 1~
12 hours, preferably 3~10 hours.In heat treatment process, carbon source (gas phase carbon source), nitrogen source (gas phase nitrogen source), hydrogen can be imported
Gas and protection gas.Wherein carbon source can use methane (CH4), acetylene (C2H2), ethene (C2H4), ethane (C2H6), propane (C3H8)、
Propylene (C3H6) or their mixed gas gaseous carbon source, nitrogen source be ammonia (NH3), protection gas can be argon gas (Ar), nitrogen
(N2), helium (He) or their mixed gas.Each gas flow can be：20~100sccm of carbon source；20~100sccm of nitrogen source；
20~100sccm of hydrogen；Protect 20~800sccm of gas.As an example, carbon source presoma is put with chemical vapour deposition technique
Be placed in tube furnace, annealed under certain atmosphere, can obtained three-dimensional porous nitrating carbon material, prepared after grinding doped with
The carbon powder material of the nitrating of tin simple substance.
In addition, in CVD growth graphene, other organic nitrogen sources can also be imported and/or can to introduce other heteroatomic
Doped source, to prepare many doping three-dimensional graphemes.Other described valuable nitrogen sources be melamine, other described hetero atoms be P, O,
S or B, the doped source is selected from, thiophene, pyrroles, borine, boron oxide, five phosphorous oxides, at least one of phosphorus chloride and boric acid,
The mole sum of the N and other foreign atoms should be less than the 20% of carbon material carbon atom integral molar quantity, namely heteroatom
Accounting is less than 20%.
Material after carbonization is put into etching liquid, metallic element is removed.As an example, tin simple substance is mixed into preparation
Carbon dust be added in acid solution (etching liquid), metal simple-substance can be etched, afterwards wash, dry the (side of the drying
Method be freeze-drying, direct boulton process, direct air drying method, or supercritical drying) obtain three-dimensional porous mix
Nitrogen carbon material.The etching liquid includes but is not limited in hydrochloric acid, sulfuric acid, perchloric acid, nitric acid, phosphoric acid, hydrofluoric acid solution at least
It is a kind of.30 DEG C~120 DEG C of etching temperature, preferably 30 DEG C~90 DEG C, etch period can be 0.5h~48h.
The present invention only needs common CVD system to be that the extensive preparation of three-dimensional porous nitrating carbon material can be achieved.According to this
The method of invention prepares the macroporous structure that three-dimensional porous its microscopic pattern of nitrating carbon material is three-dimensional UNICOM, and macropore diameter scope exists
50nm~1um changes, and also has many mesoporous and microcellular structure in macroporous structure.
As the example of the preparation method of a three-dimensional porous nitrating carbon material, preparation flow is as follows：
(1) with PEG-6000 0 (PEG-10000) be organic carbon source, stannous chloride be metal pink salt, by organic carbon source with
Stannous chloride solution is added in ethanol solution, is stirred under certain temperature (40~80 DEG C), and the stirring reaction time is 30~120
Minute；
(2) well mixed organic precursor is dried after stirring, temperature can be 20~120 DEG C, drying time can be 1~96
Hour；
(3) atmospheric pressure cvd carbonization will be carried out under organic precursor under the high temperature conditions certain atmosphere to be heat-treated；
(4) gained sample after carbonization is put into 1~12h of immersion in acid solution, filtering drying is to obtain three-dimensional porous nitrating carbon material；
(5) by gained sample assembly into electrode, electro-chemical test is carried out.
The three-dimensional porous nitrating carbon materials blanking aperture of the present invention can be in interior regulation and control in a big way, and specific surface area is big, up to 1300m2/
G, electric conductivity is good, is the suitable material of ultracapacitor, has broad application prospects in energy storage field.
(1) shows three-dimensional porous nitrating carbon material PN-900 prepared according to the methods of the invention ESEM in Fig. 1
Photo, as we can see from the figure three-dimensional network loose structure；
(2) show three-dimensional porous nitrating carbon material PN-900 prepared according to the methods of the invention stereoscan photograph in Fig. 1,
Three-dimensional network loose structure as we can see from the figure, carburizing temperature is set as 900 DEG C, and carbonization time is defined as 60 minutes.Carbonization
During process using ammonia as nitrogen source, flow control in 50sccm, methane (CH4) flow is in 50sccm, hydrogen flowing quantity exists
20sccm, argon flow amount is in 300sccm；
(3) show prepared according to the methods of the invention three-dimensional porous without nitrating carbon material (referring specifically to P1-900) in Fig. 1
Transmission electron microscope photo, from photo can with the three-dimensional porous three-dimensional network macropore without nitrating carbon material visible in detail, be situated between
Pore structure, and graphited graphene layer is can also be seen that, the number of plies is 3~6 layers；
(4) show porous nitrating carbon material PN-900 prepared by the method for present invention transmission electron microscope photo in Fig. 1, from photo
Three-dimensional porous structure can be clearly observed, has micropore and mesoporous；
Fig. 2 shows nitrogen adsorption desorption curve during metal pink salt various concentrations, and wherein P0.5-900 represents metallic tin salinity
For 0.5 mole every liter, chemical vapor deposition temperature is 900 DEG C, and it is 1 mole every liter that P1-900, which represents metallic tin salinity, chemistry
The temperature that is vapor-deposited is 900 DEG C, and it is 2 moles every liter that P2-900, which represents metallic tin salinity, and chemical vapor deposition temperature is 900
℃；
Fig. 3 shows the Raman spectrogram of three-dimensional porous nitrating carbon material prepared according to the methods of the invention, wherein Raman frequency shift
Scope is from 1000 to 3000cm-1.The position at three peaks is substantially on Raman spectrogram：D peaks 1340cm-1, G peaks 1591cm-1；
Fig. 4 shows the BET test collection of illustrative plates for three-dimensional many nitrating carbon material powders that the method according to the invention is prepared, wherein,
(a) is nitrogen adsorption-desorption curve in Fig. 4, and (b) is pore size distribution curve in Fig. 4, and that wherein P-900 refers to is PN-900 respectively
And P1-900；
Fig. 5 shows three-dimensional porous nitrating carbon material powder PN-900 prepared according to the methods of the invention as super capacitor equipment
The capacitive property test chart of material, wherein, (a) is the capacitive property under different scanning rates that cyclic voltammetry is measured in Fig. 5,
(b) is the constant current charge-discharge performance under different size charging and discharging currents in Fig. 5.Therefrom visible three-dimensional porous nitrating carbon materials feed powder
End judges that its capacity reaches 600F/g as super capacitor material by 1A/g discharge process.Meanwhile, in high discharge and recharge
Under current condition, curve shape is stable, obvious pressure drop does not occur, it can be determined that go out this three-dimensional porous nitrating carbon material have it is good
Good electric conductivity；
Fig. 6 shows three-dimensional porous nitrating carbon material powder prepared according to the methods of the invention as ultracapacitor device performance
Power-energy curve figure, it can be seen that in the case of 1A/g discharge current, its energy density is up to 12.0Wh kg-1, together
When, in 6.0kW kg-1Power density under, it still is able to keep 7.17Wh kg-1Energy density, showing it as device is
Excellent performance.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.In the present invention, pore volume, aperture and the Bi Biao being related to
Area is calculated according to Barrett-Joyner-Halenda (BJH) and Brunauer-Emmett-Teller (BET) method respectively,
Pore-size distribution is calculated according to Barrett-Joyner-Halenda (BJH) method.
The preparation of the three-dimensional porous nitrating carbon material of embodiment 1
(1) with PEG-6000 0 (PEG-10000) for organic carbon source 4g, stannous chloride is metal pink salt, by organic carbon source
It is added in 30mL ethanol solutions, is stirred at 60 DEG C of certain temperature, stirring reaction with stannous chloride solution (1mol/L, 3mL)
Time is 120 minutes；
(2) well mixed organic precursor is dried after stirring, drying temperature is 60 DEG C, drying time is 12 hours；
(3) atmospheric pressure cvd carbonization will be carried out under organic precursor under the high temperature conditions certain atmosphere to be heat-treated.Carburizing temperature is set as
900 DEG C, carbonization time is defined as 60 minutes.Process is using ammonia as nitrogen source in carbonisation, and flow is controlled in 50sccm, methane stream
Amount is in 50sccm, and hydrogen flowing quantity is in 20sccm, and argon flow amount is in 300sccm；
(4) gained sample after carbonization is put into 3mol/L hydrochloric acid acid solutions and soaks 12h, filtering drying is to obtain three-dimensional porous nitrating
Carbon material PN-900；
(5) by gained sample assembly into electrode, electro-chemical test is carried out.
The three-dimensional porous preparation without nitrating carbon material of embodiment 2
(1) with PEG-6000 0 (PEG-10000) for organic carbon source 4g, stannous chloride is metal pink salt, by organic carbon source
It is added to respectively with 5mL stannous chloride solutions (0.5mol/L, 1mol/L, 2mol/L) in 20mL ethanol solutions, in certain temperature
Stirred at 60 DEG C, the stirring reaction time is 120 minutes；
(2) well mixed organic precursor is dried after stirring, drying temperature is 60 DEG C, drying time is 12 hours；
(3) atmospheric pressure cvd carbonization will be carried out under organic precursor under the high temperature conditions certain atmosphere to be heat-treated.Carburizing temperature is set as
900 DEG C, carbonization time is defined as 60 minutes.Process control methane flow is in 50sccm in carbonisation, and hydrogen flowing quantity exists
20sccm, argon flow amount is in 300sccm；
(4) gained sample after carbonization is put into 3mol/L hydrochloric acid acid solutions and soaks 12h, filtering drying is to obtain three-dimensional porous nothing to mix
Nitrogen carbon material P0.5-900, P1-900 and P2-900, it is 0.5 mole every liter that wherein P0.5-900, which represents metallic tin salinity, is changed
It is 900 DEG C to learn vapour deposition temperature, and it is 1 mole every liter that P1-900, which represents metallic tin salinity, and chemical vapor deposition temperature is 900
DEG C, it is 2 moles every liter that P2-900, which represents metallic tin salinity, and chemical vapor deposition temperature is 900 DEG C；
(5) by gained sample assembly into electrode, electro-chemical test is carried out.
(2) institute in the stereoscan photograph such as Fig. 1 for the three-dimensional porous nitrating carbon material powder that method through the present invention is obtained
Show, therefrom visible three-dimensional net structure, macropore scope is in 50~1000nm, mesoporous 2~50nm.
The three-dimensional porous transmission electron microscope photo without nitrating carbon material powder (PN-900) that method through the present invention is obtained is such as
, can be with the three-dimensional porous three-dimensional network macropore without nitrating carbon material visible in detail, mesoporous from photo in Fig. 1 shown in (3)
Structure, and graphited graphene layer is can also be seen that, the number of plies is 3~6 layers.(4) show the method according to the invention in Fig. 1
The transmission electron microscope photo of the three-dimensional porous nitrating carbon material prepared, can have micropore, mesoporous knot from photo with visible in detail
Structure.
The BET test collection of illustrative plates such as Fig. 7 institutes for three-dimensional ordered macroporous, the mesoporous graphene powder that method through the present invention is obtained
Show；Three-dimensional porous structure, big specific surface area is the suitable material in ultracapacitor field.
The three-dimensional porous nitrating carbon material powder for preparing of method through the present invention as super capacitor material electricity
Capacitive energy test chart, as shown in Figure 5.Wherein, (a) figure is the capacitive character under different scanning rates that cyclic voltammetry is measured
Can, (b) figure is the constant current charge-discharge performance under different size charging and discharging currents.Therefrom visible three-dimensional porous nitrating carbon materials feed powder
End judges that its capacity reaches 600F/g as super capacitor material by 1A/g discharge process.Meanwhile, in high discharge and recharge
Under current condition, curve shape is stable, obvious pressure drop does not occur, it can be determined that go out this three-dimensional porous nitrating carbon material have it is good
Good electric conductivity.
The three-dimensional porous nitrating carbon material powder that method processing through the present invention is obtained is as ultracapacitor device performance
Power-energy curve figure, such as Fig. 6.In the case of 1A/g discharge current, its energy density is up to 12.0Wh kg-1, meanwhile,
In 6.0kW kg-1Power density under, it still is able to keep 7.17Wh kg-1Energy density, it is property to show it as device
Can be outstanding.
Concentration of the invention by changing metal tin-salt solution, the specific surface area of the carbon material obtained by can regulating and controlling, such as
Shown in table 1.Table 1：
The three-dimensional porous preparation without nitrating carbon material under the different carburizing temperatures of embodiment 3
(1) with PEG-6000 0 (PEG-10000) for organic carbon source 16g, stannous chloride is metal pink salt, by organic carbon source
It is added in 80mL ethanol solutions, is stirred at 60 DEG C of certain temperature with 20mL stannous chloride solutions (1mol/L) respectively, stirring
Reaction time is 120 minutes；
(2) well mixed organic precursor is dried after stirring, drying temperature is 60 DEG C, drying time is 12 hours；
(3) organic precursor is divided into 4 parts, carried out under the high temperature conditions under certain atmosphere at the atmospheric pressure cvd heat of carbonization respectively
Reason.Carburizing temperature is respectively set as 600 DEG C, 700 DEG C, 800 DEG C and 900 DEG C, and carbonization time is defined as 60 minutes.In carbonisation
Process control methane flow is in 50sccm, and hydrogen flowing quantity is in 20sccm, and argon flow amount is in 300sccm；
(4) gained all samples after carbonization are not originally put into 3mol/L hydrochloric acid acid solutions and soak 12h, filtering drying is to obtain three-dimensional
It is porous without nitrating carbon material P1-600, P1-700, P1-800 and P1-900-3, it is 1 that wherein P1-600, which represents metallic tin salinity,
Mole every liter, chemical vapor deposition temperature is 600 DEG C, and it is 1 mole every liter, chemical vapor deposition that P1-700, which represents metallic tin salinity,
Accumulated temperature degree is 700 DEG C, and it is 1 mole every liter that P1-800, which represents metallic tin salinity, and chemical vapor deposition temperature is 800 DEG C；P1-
It is 1 mole every liter that 900-3, which represents metallic tin salinity, and chemical vapor deposition temperature is 900 DEG C；
(5) by gained sample assembly into electrode, electro-chemical test is carried out.
Table 2 is the three-dimensional porous ID/IG values without nitrogen-doped carbon material that are prepared under the different carburizing temperatures of the present invention, its
Middle ID/IGRepresent degree of graphitization, ID/IGSmaller, then degree of graphitization is strong：
Fig. 7 is the three-dimensional porous Raman collection of illustrative plates without nitrogen-doped carbon material for preparing under different carburizing temperatures, from figure
Understand with the rise of carburizing temperature, D peak intensities are gradually reduced relative to G peak intensities in Raman spectrogram, and G peak intensities are gradually
Increase, illustrates that degree of graphitization gradually increases with temperature rise, by calculating ID/IG ratios, ID/IG is raised with temperature,
It is gradually reduced, further illustrates that degree of graphitization gradually increases with temperature rise.
Industrial applicability
This method is low for equipment requirements, short preparation period, and the three-dimensional porous nitrating carbon material prepared conducts electricity very well, and possesses
Abundant conductive path, specific surface area is big, and pore structure is enriched, and performance of the supercapacitor is outstanding.The three-dimensional that the present invention is prepared
Porous nitrating carbon material has broad application prospects in energy storage field.
Claims (12)
1. a kind of method for preparing three-dimensional porous nitrating carbon material, it is characterised in that including：
Organic carbon source and metal tin-salt solution are added in organic solvent, done after being stirred 30~120 minutes at 40~80 DEG C
It is dry, obtain the presoma containing metal pink salt and organic carbon source；
Presoma of the gained containing tin metal pink salt and organic carbon source is placed in the atmosphere containing gas phase carbon source, 300~
CVD carbonizations heat treatment 10 minutes~12 hours is carried out at 1000 DEG C, then obtains after acid etch three-dimensional porous nitrating carbon material.
2. according to the method described in claim 1, it is characterised in that the organic carbon source is selected from polyethylene glycol, polyvinyl pyrrole
At least one of alkanone, agar, melamine, sucrose and glucose.
3. method according to claim 1 or 2, it is characterised in that the organic solvent is in methanol, ethanol and propyl alcohol
At least one, preferably ethanol, the mass ratio of the organic carbon source and organic solvent is（2~20）：1, preferably（5~10）：
1。
4. the method according to any one of claim 1-3, it is characterised in that the metal pink salt is selected from the oxygen of metallic tin
At least one of compound, chloride, nitrate, oxalates, acetate, the concentration of the metal tin-salt solution for 0.1~
5mol/L, preferably 0.5~2mol/L.
5. the method according to any one of claim 1-4, it is characterised in that organic solvent and the metal tin-salt solution
Volume ratio be（2~30）：1, be preferably（6~10）：1.
6. the method according to any one of claim 1-5, it is characterised in that the temperature of the CVD carbonizations heat treatment is
500~900 DEG C, the time is 10 minutes~10 hours, preferably 3~10 hours.
7. the method according to any one of claim 1-6, it is characterised in that the gas that the CVD carbonizations heat treatment is passed through
Atmosphere includes：Below gas phase carbon source 100sccm, preferably 10~50sccm；Below gas phase nitrogen source 100sccm, preferably 50~80sccm；
10~100sccm of hydrogen, preferably 20~50sccm；Protect 20~800sccm of gas, preferably 20~400sccm.
8. method according to claim 7, it is characterised in that the gas phase carbon source be selected from methane, acetylene, ethene, ethane,
At least one of propane and propylene；The gas phase nitrogen source is ammonia；It is described protection gas in argon gas, nitrogen and helium extremely
Few one kind.
9. the method according to any one of claim 1-8, it is characterised in that when carrying out CVD carbonization heat treatments, also import
Other organic nitrogen sources and/or other heteroatomic doped sources can be introduced, other described valuable nitrogen sources are melamine, it is described other
Hetero atom is P, O, S or B, and the doped source is in thiophene, pyrroles, borine, boron oxide, five phosphorous oxides, phosphorus chloride and boric acid
At least one, the mole sum of the N and other foreign atoms should be less than the 20% of carbon material carbon atom integral molar quantity.
10. the method according to any one of claim 1-9, it is characterised in that use sulfuric acid, hydrochloric acid, perchloric acid, phosphorus
At least one of acid, nitric acid acid solution carries out acid etch.
11. a kind of method according to any one of claim 1-10 prepares three-dimensional porous nitrating carbon material.
12. a kind of three-dimensional porous nitrating carbon material as claimed in claim 11 is in ultracapacitor and lithium ion battery device
Using.
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